CN105765453B

CN105765453B - Aligning agent for liquid crystal and the liquid crystal expression element for having used it

Info

Publication number: CN105765453B
Application number: CN201480064518.XA
Authority: CN
Inventors: 铁谷尚士; 樱井宏之; 保坂和義
Original assignee: Nissan Chemical Corp
Current assignee: Nissan Chemical Corp
Priority date: 2013-09-26
Filing date: 2014-09-25
Publication date: 2019-04-12
Anticipated expiration: 2034-09-25
Also published as: TW201527846A; KR102255769B1; KR20160060733A; JPWO2015046374A1; TWI673548B; JP6501073B2; WO2015046374A1; CN105765453A

Abstract

Aligning agent for liquid crystal containing following (A) ingredients He (B) ingredient.(A) ingredient: the polymer containing at least any one in polyimide precursor and polyimides, the polyimide precursor and polyimides have the structure with nitrogen-atoms.(B) ingredient: the polymer containing at least any one in polyimide precursor and polyimides, the polyimide precursor and polyimides have urea structure or thiocarbamide structure.Wherein, at least one of polymer of (A) ingredient and (B) ingredient contains specific side-chain structure.

Description

Aligning agent for liquid crystal and the liquid crystal expression element for having used it

Technical field

It is handled the present invention relates to aligning agent for liquid crystal used in the manufacture for indicating element in liquid crystal, by the liquid crystal aligning The liquid crystal orientation film and the liquid crystal of the liquid crystal orientation film has been used to indicate element that agent obtains.

Background technique

Liquid crystal indicate element as realization volume it is thin/the expression equipment of light weight and now widely available.In general, the liquid Crystalline substance indicates element to determine the state of orientation of liquid crystal and uses liquid crystal orientation film.

As one of the characteristic required liquid crystal orientation film, there is the orientation inclination angle by liquid crystal molecule relative to real estate to protect Hold the pre-tilt angle for for arbitrary value, i.e. controlling liquid crystal.The size of the known pre-tilt angle can be made up of the poly- of liquid crystal orientation film selection Imido structure changes.Among the technology for controlling pre-tilt angle by the structure of polyimides, by the diamines with side chain The method of a part as polyimides raw material can control pre-tilt angle according to the use ratio of the diamines, therefore be easier to obtain Target pre-tilt angle is obtained, is useful (referring for example to patent document 1) as the means for increasing pre-tilt angle.In addition, for like this For increasing the diamine component of liquid crystal pretilt angle, also carry out grinding for the structure for improving pre-tilt angle stability, process dependency Study carefully, as side-chain structure used herein, proposes the structure comprising ring structures such as phenyl, cyclohexyl (referring for example to patent text It offers 2).

In addition, indicating inhibition, the afterimage of the contrast reduction of element from liquid crystal as liquid crystal indicates the high-definition of element From the perspective of phenomenon reduces, for liquid crystal orientation film used in it, voltage retention is high, when applying DC voltage The characteristic that accumulated charge is few or the charge accumulated by DC voltage quickly mitigates gradually becomes important.

In the liquid crystal orientation film of polyimides system, time until disappearing as the afterimage that is generated by DC voltage short liquid Brilliant alignment films, it is known that: used polyamic acid, containing the polyamic acid of imide on the basis of also containing specific knot The liquid crystal orientation film of the aligning agent for liquid crystal of the tertiary amine of structure (referring for example to patent document 3)；It has used containing soluble polyamides The liquid crystal orientation film of the aligning agent for liquid crystal of imines, the soluble polyimide is by the specific diamines with pyridine skeleton etc. For raw material (referring for example to patent document 4) etc..In addition, afterimage disappearance high as voltage retention and because of DC voltage generation Until time short liquid crystal orientation film, it is known that: used on the basis ofs polyamic acid, its imide amination polymer etc. The liquid crystal orientation film of aligning agent for liquid crystal also containing the following compound of minute quantity, the compound are selected from: intramolecular contains 1 Compound and intramolecular that the compound of a carboxylic acid group, intramolecular contain 1 acid anhydride contain the chemical combination of 1 tertiary amino Object (referring for example to patent document 5).

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 2-282726 bulletin

Patent document 2: Japanese Unexamined Patent Publication 9-278724 bulletin

Patent document 3: Japanese Unexamined Patent Publication 9-316200 bulletin

Patent document 4: Japanese Unexamined Patent Publication 10-104633 bulletin

Patent document 5: Japanese Unexamined Patent Publication 8-76128 bulletin

Summary of the invention

Problems to be solved by the invention

Liquid crystal orientation film is also used to carry out control of the liquid crystalline phase for the angle of substrate, i.e. liquid crystal pretilt angle.Especially, exist In VA (Vertical Alignment) mode, PSA (Polymer Sustained Alignment) mode etc., need to make liquid It is brilliant vertically oriented, therefore, the ability (the also referred to as vertical orientation, high pre-dumping that make liquid crystal vertical-tropism are required liquid crystal orientation film Angle).In turn, for liquid crystal orientation film, it is not only high vertical orientation, important is also become for its stability.Especially, In order to obtain high brightness and use calorific value is big, the liquid crystal of backlight more than light irradiation amount indicates element such as auto-navigation system, Large-scale tv is used or is placed in the environment of being exposed to high temperature for a long time and light irradiates sometimes.Under this critical conditions, hang down When straight orientation reduces, generates the characterization that can not obtain initial stage or indicate that the problems such as uneven occurs.

In turn, one of electrical characteristics of element i.e. voltage retention is indicated about liquid crystal, also requires above-mentioned etc harsh item High stability under part.That is, being easy to happen liquid crystal indicates element when voltage retention is reduced because being originated from the light irradiation of backlight Indicate that one of bad i.e. afterimage is bad (also referred to as line afterimage), the liquid crystal that can not obtain high reliablity indicates element.Therefore, for For liquid crystal orientation film, on the basis of requiring initial stage characteristic good, even if for example, also requiring to be exposed to light irradiation for a long time Afterwards, voltage retention is also difficult to decrease.In turn, i.e. face afterimage bad for another afterimage, also requires by being originated from backlight Light irradiation, the liquid crystal orientation film of the residual charge accumulated by DC voltage quickly mitigated.

Thus, the object of the present invention is to provide the aligning agent for liquid crystal for having both above-mentioned characteristic.That is, mesh of the invention Be, the liquid crystal orientation film that can show to stablize pre-tilt angle long-time is exposed to after high temperature and light irradiation is provided. Also, the reduction of voltage retention is able to suppress and because straight long-time is exposed to after light irradiation it is intended that providing The liquid crystal orientation film of galvanic electricity pressure and the residual charge of accumulation quickly mitigated.

Also, provide the liquid that there is the liquid crystal of above-mentioned liquid crystal orientation film to indicate element, be capable of providing above-mentioned liquid crystal orientation film Brilliant aligning agent.

In turn, the object of the present invention is to provide the liquid crystal for having the liquid crystal orientation film being consistent with above-mentioned requirements to indicate member Part.

The solution to the problem

Present inventor has performed further investigations, as a result, it has been found that: at the liquid crystal aligning with 2 kinds of polymer with specific structure Reason agent for realize above-mentioned purpose be it is extremely effective, so as to complete the present invention.

That is, the present invention has following purport.

(1) a kind of aligning agent for liquid crystal contains following (A) ingredients and (B) ingredient:

(A) ingredient: the polymer containing at least any one in polyimide precursor and polyimides, the polyamides Imines precursor and polyimides have the structure with nitrogen-atoms.

(B) ingredient: the polymer containing at least any one in polyimide precursor and polyimides, the polyamides Imines precursor and polyimides have structure shown in following formula [2].

It should be noted that at least either in the polymer of (A) ingredient and (B) ingredient contains shown in following formula [3] Structure.

(in formula [2], Y¹And Y⁷Singly-bound is each independently represented, alkylidene ,-O- ,-N (R selected from carbon number 1~10¹)-(R¹ Indicate the alkylidene of hydrogen atom or carbon number 1~3) ,-CON (R²)-(R²Indicate the alkylidene of hydrogen atom or carbon number 1~3) ,-N (R³) CO-(R³Indicate the alkylidene of hydrogen atom or carbon number 1~3) ,-CH₂At least one kind of organic group in O- ,-COO- and-OCO-；Y² And Y⁶Each independently represent the alkylidene of carbon number 1~10；Y³And Y⁵Each independently represent the Asia of hydrogen atom or carbon number 1~10 Alkyl；Y⁴Indicate oxygen atom or sulphur atom).

(in formula [3], B¹Indicate singly-bound ,-(CH₂)_a(integer that a is 1~15) ,-O- ,-CH₂O- ,-COO- or-OCO-；B² Indicate singly-bound or-(CH₂)_b(integer that b is 1~15)；B³Indicate singly-bound ,-(CH₂)_c(integer that c is 1~15) ,-O- ,- CH₂O- ,-COO- or-OCO-；B⁴It indicates the divalent cyclic group in phenyl ring, cyclohexane ring or heterocycle or there is steroids The divalent organic group of the carbon number 17~51 of skeleton, any hydrogen atom on aforementioned cyclic group optionally by the alkyl of carbon number 1~3, The alkoxy of carbon number 1~3, carbon number 1~3 replace containing fluoroalkyl, the fluoroalkoxy of carbon number 1~3 or fluorine atom；B⁵Indicate choosing From any hydrogen atom on the divalent cyclic group in phenyl ring, cyclohexane ring or heterocycle, these cyclic groups optionally by carbon number 1~3 Alkyl, the alkoxy of carbon number 1~3, carbon number 1~3 replace containing fluoroalkyl, the fluoroalkoxy of carbon number 1~3 or fluorine atom；n Indicate 0~4 integer；B⁶Indicate the alkyl of carbon number 1~18, carbon number 1~18 containing fluoroalkyl, carbon number 1~18 alkoxy or The fluoroalkoxy of carbon number 1~18).

(2) aligning agent for liquid crystal according to above-mentioned (1), wherein the structure with nitrogen-atoms in aforementioned (B) ingredient For at least one kind of structure in structure shown in following formula [1a]~formula [1c].

(in formula [1a], X¹Indicate phenyl ring or nitrogenous heteroaromatic, X²Indicate hydrogen atom or by the aliphatic of carbon number 1~12 The disubstituted amido that group replaces；In formula [1b], X³And X⁷It each independently represents with 6~15 carbon atoms and has 1~2 The aromatic group of a phenyl ring, X⁴And X⁶Each independently represent the alkylidene of hydrogen atom or carbon number 1~5, X⁵Indicate carbon number 2~5 Alkylidene or xenyl, m indicate 0 or 1 integer；In formula [1c], X⁸And X¹⁰It each independently represents selected from following formula [1c- A] and formula [1c-b] shown at least one kind of structure in structure, X⁹Indicate the alkylidene or phenyl ring of carbon number 1~5).

(3) aligning agent for liquid crystal according to above-mentioned (1) or above-mentioned (2), wherein the polymer of aforementioned (A) ingredient It is by diamine compound shown in following formula [1-1] for polymer obtained from a part of raw material.

(in formula [1-1], X^AIndicate at least one kind of structure for having in structure shown in previously described formula [1a]~formula [1c] Organic group；A¹And A²Each independently represent the alkylidene of hydrogen atom or carbon number 1~5).

(4) it is following formula [1a-1] that the aligning agent for liquid crystal according to above-mentioned (3), which is by aforementioned diamine compound, Diamine compound shown in~formula [1c-1] is for polymer obtained from a part of raw material.

(in formula [1a-1], X¹Indicate phenyl ring or nitrogenous heteroaromatic, X²Indicate hydrogen atom or by the fat of carbon number 1~12 The disubstituted amido that race's group replaces；In formula [1b-1], X³And X⁷It each independently represents with 6~15 carbon atoms and has 1 The aromatic group of~2 phenyl ring, X⁴And X⁶Each independently represent the alkylidene of hydrogen atom or carbon number 1~5, X⁵Indicate carbon number 2 ~5 alkylidene or xenyl, m indicate 0 or 1 integer；In formula [1c-1], X⁸And X¹⁰It each independently represents selected from previously described formula At least one kind of structure in structure shown in [1c-a] and formula [1c-b], X⁹Indicate the alkylidene or phenyl ring of carbon number 1~5；Formula [1a-1] In~formula [1c-1], A¹~A⁶Each independently represent the alkylidene of hydrogen atom or carbon number 1~5).

(5) aligning agent for liquid crystal according to above-mentioned (4), wherein aforementioned diamine compound is selected from following formula [1- 1a] at least one kind of diamine compound in diamine compound shown in~formula [1-4a].

(in formula [1-3a], R¹Indicate the alkylidene of hydrogen atom or carbon number 1~5；In formula [1-4a], n indicate 1~10 it is whole Number；In formula [1-1a]~formula [1-4a], A¹~A⁸Each independently represent the alkylidene of hydrogen atom or carbon number 1~5).

(6) aligning agent for liquid crystal according to any one of above-mentioned (1)~above-mentioned (5), wherein aforementioned (B) ingredient Polymer be by diamine compound shown in following formula [2-1] for raw material a part obtained from polymer.

(in formula [2-1], Y^AIndicate the organic group with structure shown in previously described formula [2]；A¹And A²It each independently represents The alkylidene of hydrogen atom or carbon number 1~5).

(7) it is following formula [2a] institute that the aligning agent for liquid crystal according to above-mentioned (6), which is by aforementioned diamine compound, The diamine compound shown is for polymer obtained from a part of raw material.

(in formula [2a], Y¹And Y⁷Singly-bound is each independently represented, alkylidene ,-O- ,-N (R selected from carbon number 1~10¹)- (R¹Indicate the alkylidene of hydrogen atom or carbon number 1~3) ,-CON (R²)-(R²Indicate the alkylidene of hydrogen atom or carbon number 1~3) ,-N (R³)CO-(R³Indicate the alkylidene of hydrogen atom or carbon number 1~3) ,-CH₂At least one kind of organic group in O- ,-COO- and-OCO- Group；Y²And Y⁶Each independently represent the alkylidene of carbon number 1~10；Y³And Y⁵Each independently represent hydrogen atom or carbon number 1~10 Alkylidene；Y⁴Indicate oxygen atom or sulphur atom；A¹And A²Each independently represent the alkylidene of hydrogen atom or carbon number 1~5).

(8) aligning agent for liquid crystal according to above-mentioned (7), wherein aforementioned diamine compound is selected from following formula [2- 1a] at least one kind of diamine compound in diamine compound shown in~formula [2-3a].

(in formula [2-1a]~formula [2-3a], A¹~A⁶Each independently represent the alkylidene of hydrogen atom or carbon number 1~5).

(9) aligning agent for liquid crystal according to any one of above-mentioned (1)~above-mentioned (8), wherein aforementioned (A) ingredient Diamine compound shown in following formula [3a] is used for a part of raw material by the polymer of at least either in (B) ingredient.

(in formula [3a], B indicates previously described formula [3]；A¹And A²Each independently represent the alkylidene of hydrogen atom or carbon number 1~5； M indicates 1~4 integer).

(10) aligning agent for liquid crystal according to any one of above-mentioned (1)~above-mentioned (9), wherein aforementioned (A) ingredient Polymer and the polymer of (B) ingredient be selected from using polyimides obtained from tetracarboxylic acid sour component shown in following formula [4] At least one kind of polymer in precursor and polyimides.

(in formula [4], Z indicates at least one kind of structure in structure shown in following formula [4a]~formula [4k]).

(in formula [4a], Z¹~Z⁴Indicate hydrogen atom, methyl, ethyl, propyl, chlorine atom or phenyl ring, it is optionally identical each other or It is different；In formula [4g], Z⁵And Z⁶Indicate hydrogen atom or methyl, optionally identical or different each other).

(11) aligning agent for liquid crystal according to above-mentioned (10), wherein aforementioned tetracarboxylic acid sour component is in previously described formula [4] Z be at least one kind of structure in structure shown in previously described formula [4a] and formula [4e]~formula [4g] tetracarboxylic acid sour component.

(12) aligning agent for liquid crystal according to any one of above-mentioned (4)~above-mentioned (11), wherein aforementioned (A) at In the polymer divided, diamine compound shown in previously described formula [1a-1]~formula [1c-1] is in 100 moles of % of whole diamine components For 5 moles of %~95 mole %.

(13) aligning agent for liquid crystal according to any one of above-mentioned (7)~above-mentioned (12), wherein aforementioned (B) at In the polymer divided, diamine compound shown in previously described formula [2a] is 5 moles of %~95 in 100 moles of % of whole diamine components Mole %.

(14) aligning agent for liquid crystal according to any one of above-mentioned (1)~above-mentioned (13), wherein aforementioned (B) at The polymer phase divided is 0.5 mass parts~950 mass parts for 100 mass parts of polymer of aforementioned (A) ingredient.

(15) aligning agent for liquid crystal according to any one of above-mentioned (1)~above-mentioned (14), wherein taken as liquid crystal To the solvent of inorganic agent, containing in n-methyl-2-pyrrolidone, N- ethyl-2-pyrrolidone and gamma-butyrolacton at least 1 kind of solvent.

(16) aligning agent for liquid crystal according to any one of above-mentioned (1)~above-mentioned (15), wherein taken as liquid crystal To the solvent of inorganic agent, containing selected from 1- hexanol, cyclohexanol, 1,2- ethylene glycol, 1,2-PD, glycol monobutyl ether, second At least one kind of solvent in glycol single-butyl ether and dipropylene glycol dimethyl ether.

(17) aligning agent for liquid crystal according to any one of above-mentioned (1)~above-mentioned (16), wherein at liquid crystal aligning Manage in agent comprising at least one kind of cross-linked compound in following cross-linked compound: have epoxy group, isocyanate group, The cross-linked compound of oxetanyl or cyclocarbonate radical；With selecting free hydroxyl, hydroxy alkyl or lower alkoxy alkane The cross-linked compound of at least one kind of substituent group in the group of base composition；And the bridging property chemical combination with polyunsaturated bond Object.

(18) a kind of liquid crystal orientation film is the processing of the liquid crystal aligning as described in any one of above-mentioned (1)~above-mentioned (17) What agent obtained.

(19) a kind of liquid crystal orientation film is using at liquid crystal aligning described in any one of above-mentioned (1)~above-mentioned (17) Agent is managed as obtained from ink-jet method.

(20) a kind of liquid crystal indicates element, with liquid crystal orientation film described in above-mentioned (18) or above-mentioned (19).

(21) liquid crystal orientation film according to above-mentioned (18) or above-mentioned (19), which is characterized in that it be used to have Indicate element with liquid crystal layer between a pair of of substrate of electrode and via the liquid crystal of following process manufacture: aforementioned a pair of of substrate it Between configure liquid-crystal composition, the liquid-crystal composition includes the polymerization polymerizeing by least one of active energy beam and heat Property compound, while between former electrodes apply voltage while make aforementioned polymeric compound polymerize.

(22) a kind of liquid crystal indicates element, which is characterized in that has liquid crystal orientation film described in above-mentioned (21).

(23) liquid crystal orientation film according to above-mentioned (18) or above-mentioned (19), which is characterized in that it be used to have Indicate element with liquid crystal layer between a pair of of substrate of electrode and via the liquid crystal of following process manufacture: aforementioned a pair of of substrate it Between configure liquid crystal orientation film, the liquid crystal orientation film includes the polymerization polymerizeing by least one of active energy beam and heat Property group, while between former electrodes apply voltage while make aforementioned polymeric radical polymerisation.

(24) a kind of liquid crystal indicates element, which is characterized in that has liquid crystal orientation film described in above-mentioned (23).

The effect of invention

Aligning agent for liquid crystal comprising 2 kinds of polymer of the invention can obtain even if be exposed to for a long time high temperature and It also can express to stablize the liquid crystal orientation film of pre-tilt angle after light irradiation, the polymer is selected from the polyimides with specific structure It is at least one kind of in precursor or polyimides.Also, voltage retention can be inhibited long-time is exposed to after light irradiation by being formed Reduction and the liquid crystal orientation film that quickly mitigates of the residual charge accumulated by DC voltage.Thus, have by liquid of the invention The liquid crystal for the liquid crystal orientation film that brilliant aligning agent obtains indicates the excellent in reliability of element, can be suitably employed in big picture and height Clearly LCD TV etc..

Specific embodiment

It is described in detail below for the present invention.

The present invention is the aligning agent for liquid crystal containing following (A) ingredients and (B) ingredient, using the aligning agent for liquid crystal Obtained from liquid crystal orientation film and liquid crystal with the liquid crystal orientation film indicate element.

A kind of aligning agent for liquid crystal contains following (A) ingredients and (B) ingredient.

(A) ingredient: the polymer containing at least any one in polyimide precursor and polyimides is (also referred to as special Determine polymer (A)), the polyimide precursor and polyimides have the structure with nitrogen-atoms.

(B) ingredient: the polymer containing at least any one in polyimide precursor and polyimides is (also referred to as special Determine polymer (B)), the polyimide precursor and polyimides have structure (also referred to as specific structure shown in following formula [2] (2))。

It should be noted that at least either in the polymer of (A) ingredient and (B) ingredient contains shown in following formula [3] Structure (also referred to as specific side-chain structure).

For the liquid crystal orientation film obtained by aligning agent for liquid crystal of the invention, about why being able to solve this hair Bright project is still not clear, it may be considered that approximately as.

That is, the previously described formula contained by least either in particular polymers (A) and particular polymers (B) of the invention [3] specific side-chain structure shown in is at side chain position with phenyl ring, cyclohexyl ring or heterocycle or with the carbon of steroid skeleton The divalent organic group of number 17~51.Compared with the prior art i.e. side-chain structure of chain alkyl for making liquid crystal vertical-tropism, these The side-chain structure of ring and organic group shows upright and outspoken structure.As a result, with the product phase of the side-chain structure of previous chain alkyl Than that can be obtained high by the liquid crystal orientation film that the aligning agent for liquid crystal with specific side-chain structure of the invention obtains and be stablized Liquid crystal vertical-tropism.

In addition, specific side-chain structure of the invention is for ultraviolet light etc. compared with the side-chain structure of previous chain alkyl Light is stable.Therefore, even if specific side-chain structure of the invention is exposed to light irradiation for a long time, also it is able to suppress voltage holding Rate reduces and inhibits the decomposition product for accumulating the side chain moiety of residual charge because of DC voltage.

In turn, it is believed that: the nitrogen in the structure with nitrogen-atoms for including in particular polymers (A) through the invention is former In son and the interaction of carboxyl (COOH yl) in particular polymers (B) and the previously described formula [2] in particular polymers (B) Nitrogen-atoms and particular polymers (A) in carboxyl interaction, the movement of charge can occur between them.With this phase Companion, the residual charge accumulated can be effectively in the intramolecular of polymer or intermolecular movements.It can think: can promote The removal of the residual charge as caused by DC voltage.

And it is possible to think: the structure with nitrogen-atoms in particular polymers (A) of the invention, which can capture, protects voltage The main reason for holdup reduces, that is, ionic impurity ingredient.That is, liquid crystal indicates that element can be captured because being exposed to illumination for a long time The ionic impurity penetrated and generated, along with this, being able to suppress the reduction of voltage retention.

From the viewpoint of above, of the invention is sub- selected from the polyimide precursor with specific structure or polyamides comprising 2 kinds The aligning agent for liquid crystal of at least one kind of polymer in amine can be obtained even if after being exposed to high temperature and light irradiation for a long time Also it can express and to stablize the liquid crystal orientation film of pre-tilt angle.Also, electricity can be inhibited long-time is exposed to after light irradiation by being formed The liquid crystal orientation film that the reduction of pressure conservation rate and the residual charge accumulated by DC voltage quickly mitigate.

Particular polymers (A) of the invention are containing at least any one in polyimide precursor and polyimides Polymer, the polyimide precursor and polyimides have the structure with nitrogen-atoms.

As the specific structure of the structure with nitrogen-atoms, structure shown in following formula [1a]~formula [1c] can be enumerated.

In formula [1a], X¹Indicate phenyl ring or nitrogenous heteroaromatic.

In formula [1a], X²The disubstituted amido for indicating hydrogen atom or being replaced by the aliphatic group of carbon number 1~12.

It should be noted that in formula [1a], X²When for hydrogen atom, X¹Indicate nitrogenous heteroaromatic；X²For by carbon number 1~ When the disubstituted amido that 12 aliphatic group replaces, X¹Indicate phenyl ring.

In formula [1b], X³And X⁷It each independently represents with 6~15 carbon atoms and with the aromatic series of 1~2 phenyl ring Group.

In formula [1b], X⁴And X⁶Each independently represent the alkylidene of hydrogen atom or carbon number 1~5.

In formula [1b], X⁵Indicate the alkylidene or xenyl of carbon number 2~5.

In formula [1b], m indicates 0 or 1 integer.

In formula [1c], X⁸And X¹⁰It each independently represents in structure shown in following formula [1c-a] and formula [1c-b] extremely Few a kind of structure.

In formula [1c], X⁹Indicate the alkylidene or phenyl ring of carbon number 1~5.

Particular polymers (B) of the invention are to contain at least any one in polyimide precursor and polyimides Polymer, the polyimide precursor and polyimides have specific structure shown in following formula [2].

In formula [2], Y¹And Y⁷Singly-bound is each independently represented, alkylidene ,-O- ,-S- ,-N (R selected from carbon number 1~10¹)- (R¹Indicate the alkylidene of hydrogen atom or carbon number 1~3) ,-CON (R²)-(R²Indicate the alkylidene of hydrogen atom or carbon number 1~3) ,-N (R³)CO-(R³Indicate the alkylidene of hydrogen atom or carbon number 1~3) ,-CH₂At least one kind of organic group in O- ,-COO- and-OCO- Group.Wherein, preferably singly-bound ,-O- ,-S- ,-OCO- or-COO-.From the sight of liquid crystal aligning and the film hardness of liquid crystal orientation film Point sets out, more preferably singly-bound ,-O- or-S-.

In formula [2], Y²And Y⁶Each independently represent the alkylidene of carbon number 1~10.Wherein, the preferably Asia of carbon number 1~3 Alkyl, structure can be any one of linear chain or branched chain.Specifically, the film from liquid crystal aligning and liquid crystal orientation film is hard From the perspective of degree, preferably has and rotate freely position and small structure i.e. the methylene (- CH of steric hindrance₂), ethylidene (- CH₂CH₂), propylidene (- (CH₂)₃) or isopropyl (- C (CH₂)₂-)。

In formula [2], Y³And Y⁵Each independently represent the alkyl of hydrogen atom or carbon number 1~10.Wherein, preferably hydrogen atom Or the alkyl of carbon number 1~3.Particularly preferably hydrogen atom.

In formula [2], Y⁴Indicate oxygen atom or sulphur atom.Wherein, from the viewpoint of the film hardness of liquid crystal orientation film, preferably For oxygen atom.

Previously described formula [3] institute contained by least either in particular polymers (A) and particular polymers (B) of the invention The specific side-chain structure shown is structure shown in following formula [3].

In formula [3], B¹Indicate singly-bound ,-(CH₂)_a(integer that a is 1~15) ,-O- ,-CH₂O- ,-COO- or-OCO-.Its In, from the viewpoint of raw material availability, synthesis easness, preferably singly-bound ,-(CH₂)_a(integer that a is 1~15) ,-O- ,- CH₂O- or-COO-.More preferably singly-bound ,-(CH₂)_a(integer that a is 1~10) ,-O- ,-CH₂O- or-COO-.

In formula [3], B²Indicate singly-bound or-(CH₂)_b(integer that b is 1~15).Wherein, preferably singly-bound or-(CH₂)_b- (integer that b is 1~10).

In formula [3], B³Indicate singly-bound ,-(CH₂)_c(integer that c is 1~15) ,-O- ,-CH₂O- ,-COO- or-OCO-.Its In, from the viewpoint of synthesizing easness, preferably singly-bound ,-(CH₂)_c(integer that c is 1~15) ,-O- ,-CH₂O- or- COO-.More preferably singly-bound ,-(CH₂)_c(integer that c is 1~10) ,-O- ,-CH₂O- or-COO-.

In formula [3], B⁴For the divalent cyclic group in phenyl ring, cyclohexane ring or heterocycle, appointing on these cyclic groups Meaning hydrogen atom is optionally contained by the alkyl of carbon number 1~3, the alkoxy of carbon number 1~3, carbon number 1~3 containing fluoroalkyl, carbon number 1~3 Fluoroalkyloxy or fluorine atom replace.In turn, B⁴It can be in the organic group selected from the carbon number 17~51 with steroid skeleton Divalent organic group.Wherein, from the viewpoint of synthesizing easness, preferably phenyl ring, cyclohexane ring or have steroid skeleton Carbon number 17~51 organic group.

In formula [3], B⁵Divalent cyclic group in phenyl ring, cyclohexane ring or heterocycle is indicated, on these cyclic groups Any hydrogen atom optionally by the alkyl of carbon number 1~3, the alkoxy of carbon number 1~3, carbon number 1~3 containing fluoroalkyl, carbon number 1~3 Fluoroalkoxy or fluorine atom replace.Wherein, preferably phenyl ring or cyclohexane ring.

In formula [3], n indicates 0~4 integer.Wherein, from the viewpoint of raw material availability, synthesis easness, preferably 0~3.More preferably 0~2.

In formula [3], B⁶Indicate the alkyl of carbon number 1~18, carbon number 1~18 containing fluoroalkyl, carbon number 1~18 alkoxy or The fluoroalkoxy of carbon number 1~18.Wherein, preferably the alkyl of carbon number 1~18, carbon number 1~10 containing fluoroalkyl, carbon number 1~ 18 alkoxy or the fluoroalkoxy of carbon number 1~10.The more preferably alkoxy of the alkyl of carbon number 1~12 or carbon number 1~12. The particularly preferably alkoxy of the alkyl of carbon number 1~9 or carbon number 1~9.

As the B in formula [3]¹~B⁶With the preferred combination of n, can enumerate and International Publication bulletin WO2011/132751 The identical combination of (2-1)~(2-629) disclosed in 6~table of table 47 of page 13 of (2011.10.27 is disclosed)~page 34.It needs Illustrate, the B in each table of International Publication bulletin, in the present invention¹~B⁶It is considered Y1~Y6, but Y1~Y6 can be regarded as B¹ ~B⁶.In addition, of the invention has steroid skeleton in (2-605)~(2-629) disclosed in each table of International Publication bulletin The organic group of carbon number 17~51 be considered the organic group of the carbon number 12~25 with steroid skeleton, but there is steroids The organic group of the carbon number 12~25 of skeleton can be regarded as the organic group of the carbon number 17~51 with steroid skeleton.

Particular polymers (A) and particular polymers (B) of the invention are (also to unite selected from polyimide precursor and polyimides Referred to as polyimides based polymer) at least one kind of polymer.Wherein, polyimides based polymer of the invention preferably makes Polyimide precursor obtained from diamine component is reacted with tetracarboxylic acid sour component or polyimides.

Polyimide precursor refers to structure shown in following formula [A].

(in formula [A], R¹For 4 valence organic groups, R²For divalent organic group, A¹And A²Each independently represent hydrogen atom or The alkylidene of carbon number 1~5, A³And A⁴The alkylidene or acetyl group of hydrogen atom, carbon number 1~5 are each independently represented, n indicates just whole Number).

As aforementioned diamine component, diamine compound of the intramolecular with 2 primary amino groups or secondary amino group can be enumerated.

In addition, tetracarboxylic compound, tetracarboxylic dianhydride, tetrabasic carboxylic acid dihalide can be enumerated as aforementioned tetracarboxylic acid sour component Object, tetracarboxylic acid acid dialkyl ester compound or tetracarboxylic acid acid dialkyl ester dihalide.

A in formula [A] in order to obtain¹And A²It, can be by making that there are 2 in previous molecular for the polyamic acid of hydrogen atom The diamine compound of primary amino group or secondary amino group is reacted and is obtained with tetracarboxylic compound or tetracarboxylic anhydride.

A in formula [A] in order to obtain¹And A²For the polyamic acid Arrcostab of the alkylidene of carbon number 1~5, can be by making before Diamine compound is stated to react with tetracarboxylic acid acid ihalide, tetracarboxylic acid acid dialkyl ester compound or tetracarboxylic acid acid dialkyl ester dihalide And it obtains.Alternatively, it is also possible to A shown in the introducing-type [A] into the polyamic acid obtained using preceding method¹And A²Carbon number 1~ 5 alkylidene.

Particular polymers (A) of the invention are the polymer with the structure with nitrogen-atoms.Wherein, preferably previously described formula Structure shown in [1a]~formula [1c].

The method that structure with nitrogen-atoms is directed into particular polymers (A) is not particularly limited, before preferably having The diamine compound for stating structure shown in formula [1a]~formula [1c] is used for a part of raw material.

Specifically, it is preferable that using diamine compound (also referred to as specific diamine compound shown in following formula [1-1] (1))。

In formula [1-1], X^AIndicate the carbon at least one kind of structure for having in structure shown in previously described formula [1a]~formula [1c] The organic group of number 5~50.

In formula [1-1], A¹And A²Each independently represent the alkylidene of hydrogen atom or carbon number 1~5.

More specifically, it is preferable to use diamine compound shown in following formula [1a-1]~formula [1c-1].

In formula [1a-1], X¹Indicate phenyl ring or nitrogenous heteroaromatic.

In formula [1a-1], X²The disubstituted amido for indicating hydrogen atom or being replaced by the aliphatic group of carbon number 1~12.

It should be noted that in formula [1a-1], X²When for hydrogen atom, X¹Indicate nitrogenous heteroaromatic；X²For by carbon number 1 When the disubstituted amido that~12 aliphatic group replaces, X¹Indicate phenyl ring.

In formula [1b-1], X³And X⁷It each independently represents with 6~15 carbon atoms and with the fragrance of 1~2 phenyl ring Race's group.

In formula [1b-1], X⁴And X⁶Each independently represent the alkylidene of hydrogen atom or carbon number 1~5.

In formula [1b-1], X⁵Indicate the alkylidene or xenyl of carbon number 2~5.

In formula [1b-1], m indicates 0 or 1 integer.

In formula [1c-1], X⁸And X¹⁰It each independently represents in structure shown in following formula [1c-a] and formula [1c-b] At least one kind of structure.

In formula [1c-1], X⁹Indicate the alkylidene or phenyl ring of carbon number 1~5.

As the specific diamine compound of specific diamine compound (1) of the invention, following formula [1-1a] can be enumerated Diamine compound shown in~formula [1-4a].

In formula [1-3a], R¹Indicate the alkylidene of hydrogen atom or carbon number 1~5.

In formula [1-4a], n indicates 1~10 integer.

In formula [1-1a]~formula [1-4a], A¹~A⁸Each independently represent the alkylidene of hydrogen atom or carbon number 1~5.

Wherein, it is preferable to use diamine compound shown in previously described formula [1-3a] or formula [1-4a].

Specific diamine compound (1) in particular polymers (A) of the invention is excellent in 100 moles of % of whole diamine components It is selected as 1 mole of %~95 mole %.Wherein, preferably 5 moles of %~95 mole %.More preferably 20 moles of %~80 are rubbed You are %.

Specific diamine compound (1) of the invention can also be with particular polymers according to the present invention (A) in a solvent molten Xie Xing, the coating of aligning agent for liquid crystal, liquid crystal aligning when being made liquid crystal orientation film, voltage retention, accumulated charge Etc. characteristics and using a kind or mix two or more use.

Particular polymers (B) of the invention are the polymer with specific structure (2).

The method that specific structure (2) of the invention is directed into particular polymers (B) is not particularly limited, it preferably will tool There is the diamine compound of specific structure (2) for diamine component.Particularly preferably using the diamines with structure shown in previously described formula [2] Compound.

Specifically, it is preferable that using diamine compound (also referred to as specific diamine compound shown in following formula [2-1] (2))。

In formula [2-1], Y^AIndicate the organic group with structure shown in previously described formula [2].

In formula [2-1], A¹And A²Each independently represent the alkylidene of hydrogen atom or carbon number 1~5.

More specifically, it is preferable to use diamine compound shown in following formula [2a].

In formula [2a], Y¹And Y⁷Singly-bound is each independently represented, alkylidene ,-O- ,-S- ,-N selected from carbon number 1~10 (R¹)-(R¹Indicate the alkylidene of hydrogen atom or carbon number 1~3) ,-CON (R²)-(R²Indicate the alkylene of hydrogen atom or carbon number 1~3 Base) ,-N (R³)CO-(R³Indicate the alkylidene of hydrogen atom or carbon number 1~3) ,-CH₂At least one kind of in O- ,-COO- and-OCO- has Machine group.Wherein, preferably singly-bound ,-O- ,-S- ,-OCO- or-COO-.From the viewpoint of liquid crystal aligning and film hardness, more Preferably structure, that is, singly-bound ,-O- or-S- as soft and small steric hindrance as possible.

In formula [2a], Y²And Y⁶Each independently represent the alkylidene of carbon number 1~10.Wherein, the preferably Asia of carbon number 1~3 Alkyl, structure can be any one of linear chain or branched chain.Specifically, the film from liquid crystal aligning and liquid crystal orientation film is hard From the perspective of degree, preferably has and rotate freely position and small structure i.e. the methylene (- CH of steric hindrance₂), ethylidene (- CH₂CH₂), propylidene (- (CH₂)₃) or isopropyl (- C (CH₂)₂-)。

In formula [2a], Y³And Y⁵Each independently represent the alkyl of hydrogen atom or carbon number 1~10.Wherein, preferably hydrogen atom Or the alkyl of carbon number 1~3.Particularly preferably hydrogen atom.

In formula [2a], Y⁴Indicate oxygen atom or sulphur atom.Wherein, excellent from the viewpoint of the film hardness of liquid crystal orientation film It is selected as oxygen atom.

Y in formula [2a]¹、Y²、Y³、Y⁴、Y⁵、Y⁶And Y⁷Preferred combination it is as described in Table 1.

[table 1]

Y¹

Y²

Y³

Y⁴

Y⁵

Y⁶

Y⁷

2-1a

Singly-bound

-CH2-

Hydrogen atom

Oxygen atom

Hydrogen atom

-CH2-

Singly-bound

2-2a

-O-

-CH2-

Hydrogen atom

Oxygen atom

Hydrogen atom

-CH2-

-O-

2-3a

-S-

-CH2-

Hydrogen atom

Oxygen atom

Hydrogen atom

-CH2-

-S-

2-4a

Singly-bound

-CH2CH2-

Hydrogen atom

Oxygen atom

Hydrogen atom

-CH2CH2-

Singly-bound

2-5a

-O-

-CH2CH2-

Hydrogen atom

Oxygen atom

Hydrogen atom

-CH2CH2-

-O-

2-6a

-S-

-CH2CH2-

Hydrogen atom

Oxygen atom

Hydrogen atom

-CH2CH2-

-S-

2-7a

Singly-bound

-(CH2)3-

Hydrogen atom

Oxygen atom

Hydrogen atom

-(CH2)3-

Singly-bound

2-8a

-O-

-(CH2)3-

Hydrogen atom

Oxygen atom

Hydrogen atom

-(CH2)3-

-O-

2-9a

-S-

-(CH2)3-

Hydrogen atom

Oxygen atom

Hydrogen atom

-(CH2)3-

-S-

2-10a

Singly-bound

-(CH3)2-

Hydrogen atom

Oxygen atom

Hydrogen atom

-(CH3)2-

Singly-bound

2-11a

-O-

-(CH3)2-

Hydrogen atom

Oxygen atom

Hydrogen atom

-(CH3)2-

-O-

2-12a

-S-

-(CH3)2-

Hydrogen atom

Oxygen atom

Hydrogen atom

-(CH3)2-

-S-

Wherein, preferably shown in formula [2-1a], formula [2-2a], formula [2-4a], formula [2-5a], formula [2-7a] and formula [2-8a] Combination.

In formula [2a], A¹And A²Each independently represent the alkylidene of hydrogen atom or carbon number 1~5.

As the specific diamine compound of specific diamine compound (2) of the invention, following formula [2-1a] can be enumerated Diamine compound shown in~formula [2-3a].

Specific diamine compound (2) in particular polymers (B) of the invention is excellent in 100 moles of % of whole diamine components It is selected as 1 mole of %~95 mole %.Wherein, preferably 5 moles of %~95 mole %.More preferably 20 moles of %~80 are rubbed You are %.

Specific diamine compound (2) of the invention can particular polymers (B) according to the present invention dissolubility in a solvent, The characteristics such as the coating of aligning agent for liquid crystal, liquid crystal aligning, voltage retention, accumulated charge when being made liquid crystal orientation film And using a kind or mix two or more use.

At least either in particular polymers (A) and particular polymers (B) of the invention contains specific side-chain structure.

The method that specific side-chain structure of the invention is directed into particular polymers (A) or particular polymers (B) is not had It is particularly limited to, the diamine compound with specific side-chain structure is preferably used for diamine component.

Specifically, it is preferable that using (the also referred to as specific side chain type diamine chemical combination of diamine compound shown in following formula [3a] Object).

In formula [3a], B indicates previously described formula [3].It should be noted that the B in formula [3]¹~B⁶It is as above with the preferred combination of n It is shown.

In formula [3a], A¹And A²Each independently represent the alkylidene of hydrogen atom or carbon number 1~5.Wherein, preferably hydrogen is former The alkylidene of son or carbon number 1 or 2.

In formula [3a], m indicates 1~4 integer.Wherein, preferably 1.

Specific enumerable such as following formula [3a-1]~formula [3a-31] institute out of specific side chain type diamine compound of the invention The diamine compound shown and these amino are the diamine compound of secondary amino group.

(in formula [3a-1]~formula [3a-3], R¹、R³And R⁵Each independently represent-O- ,-OCH₂-、-CH₂O-、-COOCH₂- Or-CH₂OCO-；In formula [3a-1]~formula [3a-3], R²、R⁴And R⁶Each independently represent the straight-chain or branch of carbon number 1~22 The straight-chain or branched fluorine-containing of the alkylidene of shape, the straight-chain of carbon number 1~22 or branched alkoxy, carbon number 1~22 Alkylidene or fluoroalkoxy).

(in formula [3a-4]~formula [3a-6], R¹、R³And R⁵Each independently represent-COO- ,-OCO- ,-CONH- ,- NHCO-、-COOCH₂-、-CH₂OCO-、-CH₂O-、-OCH₂Or-CH₂-；In formula [3a-4]~formula [3a-6], R²、R⁴And R⁶Respectively Independently indicate the straight-chain or branched alkylidene, the straight-chain of carbon number 1~22 or branched alcoxyl of carbon number 1~22 Base, the straight-chain of carbon number 1~22 or branched fluorine-containing alkylidene or fluoroalkoxy).

(in formula [3a-7] and formula [3a-8], R¹And R³Each independently represent-COO- ,-OCO- ,-CONH- ,-NHCO- ,- COOCH₂-、-CH₂OCO-、-CH₂O-、-OCH₂-、-CH₂,-O- or-NH-；R²And R⁴Each independently represent fluorine-based, cyano, three Fluoromethane base, nitro, azo group, formoxyl, acetyl group, acetoxyl group or hydroxyl).

(in formula [3a-9] and formula [3a-10], R¹And R²Each independently represent the straight-chain or branched of carbon number 3~12 Alkylidene, Isosorbide-5-Nitrae-cyclohexylene cis-trans isomerization is respectively transisomer).

(in formula [3a-11] and formula [3a-12], R¹And R²Each independently represent the straight-chain or branched of carbon number 3~12 Alkylidene, Isosorbide-5-Nitrae-cyclohexylene cis-trans isomerization is respectively transisomer).

(in formula [1a-13], A⁴For the straight-chain of carbon number 3~20 being optionally replaced by fluorine atoms or branched alkyl, A³ For Isosorbide-5-Nitrae-cyclohexylene or Isosorbide-5-Nitrae-phenylene, A²For oxygen atom or-COO-* (wherein, the key and A of subsidiary " * "³It is bonded), A¹ For oxygen atom or-COO-* (wherein, the key and (CH of subsidiary " * "₂) a2) be bonded).In addition, a¹For 0 or 1 integer, a²It is 2 ~10 integer, a³Integer for 0 or 1).

In above-mentioned formula [3a-1]~[3a-31], the diamine compound of particularly preferred structure be formula [3a-1]~formula [3a-6], Formula [3a-9]~formula [3a-13] or formula [3a-22]~formula [3a-31].

Specific side chain type diamine compound of the invention can be used in particular polymers (A) and particular polymers (B) At least any one, can be used for two kinds of particular polymers.Wherein, it is preferred for particular polymers (A).

Specific side chain type diamine compound in particular polymers (A) and/or particular polymers (B) of the invention is preferably 10 moles of % or more and 80 mole of % or less of diamine component entirety.Particularly preferably 10 moles of % or more and 70 mole of % with Under.

Specific side chain type diamine compound of the invention can also particular polymers (A) according to the present invention and particular polymers (B) in a solvent the coating of dissolubility, aligning agent for liquid crystal, liquid crystal aligning when being made liquid crystal orientation film, voltage The characteristics such as conservation rate, accumulated charge and using a kind or mix two or more use.

As the diamine component of particular polymers (A) and particular polymers (B) of the invention, effect of the present invention is not being damaged In the range of, specific diamine compound (1), specific diamine compound (2) and specific side chain type diamine compound also can be used Other diamine compounds (also referred to as other diamine compounds) in addition.

Specifically, can enumerate 2,4- dimethyl-m-phenylenediamine, 2,6- diaminotoluene, m-phenylene diamine (MPD), p-phenylenediamine, 4,4 '-benzidines, 3,3 '-dimethyl -4,4 '-benzidine, 3,3 '-dimethoxy-4 's, 4 '-benzidines, 3, 3 '-dihydroxy -4,4 '-benzidine, 3,3 '-dicarboxyls -4,4 '-benzidine, 3,3 '-two fluoro- 4,4 '-biphenyl, 3, 3 '-trifluoromethyls -4,4 '-benzidine, 3,4 '-benzidines, 3,3 '-benzidines, 2,2 '-benzidines, 2,3 '-benzidines, 4,4 '-diaminodiphenyl-methanes, 3,3 '-diaminodiphenyl-methanes, 3,4 '-diamino-diphenyls Methane, 2,2 '-diaminodiphenyl-methanes, 2,3 '-diaminodiphenyl-methanes, 4,4 '-diamino-diphenyl ethers, 3,3 '-two Aminodiphenyl base ether, 3,4 '-diamino-diphenyl ethers, 2,2 '-diamino-diphenyl ethers, 2,3 '-diamino-diphenyl ethers, 4, 4 '-sulfonyldianilines, 3,3 '-sulfonyldianilines, bis- (4- aminophenyl) silane, bis- (3- aminophenyl) silane, diformazan Bis- (4- aminophenyl) silane of base-, bis- (3- aminophenyl) silane of dimethyl-, 4,4 '-phenothiazines, 3,3 '-thio hexichol Amine, 4,4 '-diamino-diphenyl amine, 3,3 '-diamino-diphenyl amine, 3,4 '-diamino-diphenyl amine, 2,2 '-diamino two Phenyl amine, 2,3 '-diamino-diphenyl amine, N- methyl (4,4 '-diamino-diphenyl) amine, N- methyl (3,3 '-diamino hexichol Base) amine, N- methyl (3,4 '-diamino-diphenyl) amine, N- methyl (2,2 '-diamino-diphenyl) amine, N- methyl (2,3 '-two Aminodiphenyl base) amine, 4,4 '-diaminobenzophenones, 3,3 '-diaminobenzophenones, 3,4 '-diaminobenzophenones, 1, 4- diaminonaphthalene, 2,2 '-diaminobenzophenones, 2,3 '-diaminobenzophenones, 1,5- diaminonaphthalene, 1,6- diaminonaphthalene, 1,7- diaminonaphthalene, 1,8- diaminonaphthalene, 2,5- diaminonaphthalene, 2,6- diaminonaphthalene, 2,7- diaminonaphthalene, 2,8- diamino Bis- (4- aminophenyl) ethane of naphthalene, 1,2-, bis- (3- aminophenyl) ethane of 1,2-, 1,3- bis- (4- aminophenyl) propane, 1,3- Bis- (4- aminophenyl) butane of bis- (3- aminophenyl) propane, 1,4-, bis- (3- aminophenyl) butane of 1,4-, bis- (3,5- diethyls Base -4- aminophenyl) methane, bis- (4- amino-benzene oxygen) benzene of 1,4-, bis- (4- amino-benzene oxygen) benzene of 1,3-, bis- (the 4- ammonia of 1,4- Base phenyl) benzene, bis- (4- aminophenyl) benzene of 1,3-, bis- (4- aminobenzyl) benzene of 1,4-, 1,3- bis- (4- amino-benzene oxygen) benzene, 4, 4 '-[1,4- phenylene is bis- (methylene)] diphenylamines, 4,4 '-[1,3- phenylene is bis- (methylene)] diphenylamines, 3,4 '-[1,4- Phenylene is bis- (methylene)] diphenylamines, 3,4 '-[1,3- phenylene is bis- (methylene)] diphenylamines, 3,3 '-[1,4- phenylenes pair (methylene)] diphenylamines, 3,3 '-[1,3- phenylene is bis- (methylene)] diphenylamines, bis- [(4- aminophenyl) first of 1,4- phenylene Ketone], 1,4- phenylene bis- [(3- aminophenyl) ketones], 1,3- phenylene bis- [(4- aminophenyl) ketones], 1,3- phenylene Bis- [(3- aminophenyl) ketones], 1,4- phenylene bis- (4-aminobenzoic acid esters), bis- (the 3- aminobenzoic acids of 1,4- phenylene Ester), 1,3- phenylene bis- (4-aminobenzoic acid esters), 1,3- phenylene bis- (3- Aminobenzoates), bis- (4- aminophenyls) Terephthalate, bis- (3- aminophenyl) terephthalates, bis- (4- aminophenyl) isophthalic acid esters, bis- (3- amino Phenyl) isophthalic acid ester, N, N '-(1,4- phenylene) bis- (4- aminobenzamides), N, N '-(1,3- phenylene) bis- (4- Aminobenzamide), N, N '-(1,4- phenylene) bis- (3-ABs), N, N '-(1,3- phenylene) bis- (3- amino Benzamide), N, N '-bis- (4- aminophenyl) p dimethylamines, N, N '-bis- (3- aminophenyl) p dimethylamines, N, N '-is bis- (4- aminophenyl) m-xylene diamine, N, bis- (3- aminophenyl) m-xylene diamines of N '-, 9,10- bis- (4- aminophenyl) anthracenes, 4, 4 '-bis- (4- amino-benzene oxygen) diphenyl sulfones, 2,2 '-bis- [4- (4- amino-benzene oxygen) phenyl] propane, 2,2 '-bis- [4- (4- ammonia Phenoxyl) phenyl] hexafluoropropane, 2,2 '-bis- (4- aminophenyl) hexafluoropropane, 2,2 '-bis- (3- aminophenyl) hexafluoros third Alkane, 2,2 '-bis- (3- amino -4- aminomethyl phenyl) hexafluoropropane, 2,2 '-bis- (4- aminophenyl) propane, 2,2 '-bis- (3- amino Phenyl) propane, 2,2 '-bis- (3- amino -4- aminomethyl phenyl) propane, bis- (4- amino-benzene oxygen) propane of 1,3-, bis- (the 3- ammonia of 1,3- Phenoxyl) propane, bis- (4- amino-benzene oxygen) butane of 1,4-, bis- (3- amino-benzene oxygen) butane of 1,4-, bis- (the 4- amino of 1,5- Phenoxy group) pentane, bis- (3- amino-benzene oxygen) pentanes of 1,5-, bis- (4- amino-benzene oxygen) hexanes of 1,6-, bis- (the 3- aminobenzenes of 1,6- Oxygroup) hexane, bis- (4- amino-benzene oxygen) heptane of 1,7-, 1,7- (3- amino-benzene oxygen) heptane, bis- (the 4- aminobenzene oxygen of 1,8- Base) octane, bis- (3- amino-benzene oxygen) octanes of 1,8-, bis- (4- amino-benzene oxygen) nonanes of 1,9-, bis- (the 3- aminobenzene oxygen of 1,9- Base) nonane, 1,10- (4- amino-benzene oxygen) decane, 1,10- (3- amino-benzene oxygen) decane, 1,11- (4- amino-benzene oxygen) ten One alkane, 1,11- (3- amino-benzene oxygen) hendecane, 1,12- (4- amino-benzene oxygen) dodecane, 1,12- (3- amino-benzene oxygen) Dodecane, bis- (4- aminocyclohexyl) methane, bis- (4- amino -3- methylcyclohexyl) methane, 1,3- diaminopropanes, 1,4- bis- Butylamine, 1,5- 1,5-DAP, 1,6- diamino hexane, 1,7- diaminoheptane, 1,8- diamino-octane, 1,9- diamino Base nonane, 1,10- diamino decane, 1,11- diamino undecane or 1,12- diamino dodecane and these amino are secondary The diamine compound of amino.

In turn, the diamine compound with carboxyl (COOH yl), hydroxyl (OH yl) also can be used in diamine compound.

Specifically, 2,4- diaminophenol, 3,5- diaminophenol, 3,5- diamino benzylalcohol, 2,4- bis- can be enumerated Aminobenzyl alcohol, 4,6- diamino resorcin, 2,4- diaminobenzoic acid, 2,5- diaminobenzoic acid or 3,5- diaminobenzene first Acid.Wherein, preferably 2,4- diaminobenzoic acid, 2,5- diaminobenzoic acid or 3,5- diaminobenzoic acid.Alternatively, it is also possible to It is the diamine compound of secondary amino group using diamine compound shown in following formula [3b-1]~formula [3b-4] and these amino.

(in formula [3b-1], A¹Indicate singly-bound ,-CH₂-、-C₂H₄-、-C(CH₃)₂-、-CF₂-、-C(CF₃)₂-、-O-、-CO-、- NH-、-N(CH₃)-、-CONH-、-NHCO-、-CH₂O-、-OCH₂-、-COO-、-OCO-、-CON(CH₃)-or-N (CH₃) CO-, m¹ And m²Each independently represent 0~4 integer, and m¹+m²Indicate 1~4 integer；In formula [3b-2], m³And m⁴Each independently Indicate 1~5 integer；In formula [3b-3], A²Indicate the straight chain of carbon number 1~5 or the alkylidene of branch, m⁵Indicate 1~5 integer； In formula [3b-4], A³And A⁴Each independently represent singly-bound ,-CH₂-、-C₂H₄-、-C(CH₃)₂-、-CF₂-、-C(CF₃)₂-、-O-、- CO-、-NH-、-N(CH₃)-、-CONH-、-NHCO-、-CH₂O-、-OCH₂-、-COO-、-OCO-、-CON(CH₃)-or-N (CH₃) CO-, m⁶Indicate 1~4 integer).

Also, also can be used in diamine compound have following formula [3c] shown in nitrogenous heterocyclic diamine compound and These amino are the diamine compound of secondary amino group.

In formula [3c], D¹Expression-O- ,-NH- ,-N (CH₃)-、-CONH-、-NHCO-、-CH₂O-、-OCO-、-CON(CH₃)- Or-N (CH₃)CO-.Wherein ,-O- ,-NH- ,-CONH- ,-NHCO- ,-CH₂O-、-OCO-、-CON(CH₃)-or-N (CH₃) CO- appearance It is easily-synthesized diamine compound, so it is preferred that.More preferably-O- ,-NH- ,-CONH- ,-NHCO- ,-CH₂O- ,-OCO- or-CON (CH₃)-.Particularly preferably-O- ,-CONH- or-CH₂O-。

In formula [3c], D²Indicate singly-bound, the aliphatic alkyl of carbon number 1~20, non-aromatic ring type alkyl or aromatic hydrocarbon Base.

The aliphatic alkyl of carbon number 1~20 can be straight-chain, or branched.Furthermore it is possible to have unsaturation Key.Wherein, the preferably alkylidene of carbon number 1~10.

As the concrete example of non-aromatic alkyl, can enumerate cyclopropane ring, cyclobutane ring, pentamethylene ring, cyclohexane ring, Cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, ring hendecane ring, cyclododecane ring, ring tridecane ring, the ring tetradecane Ring, cyclopentadecane ring, ring hexadecane ring, ring heptadecane ring, ring octadecane ring, ring nonadecane ring, ring icosane ring, tricyclic two Decane ring, tricyclic docosane ring, norbornane ring, decahydro naphthalene nucleus, norbornene ring or adamantane ring etc..Wherein, preferably For cyclopropane ring, cyclobutane ring, pentamethylene ring, cyclohexane ring, cycloheptane ring, norbornene ring or adamantane ring.

As the concrete example of aromatic hydrocarbyl, phenyl ring, naphthalene nucleus, tetrahydric naphthalene ring, azulenes, indenes ring, fluorenes ring, anthracene can be enumerated Ring, phenanthrene ring or that non-alkene ring etc..Wherein, preferably phenyl ring, naphthalene nucleus, tetrahydric naphthalene ring, fluorenes ring or anthracene nucleus.

As the preferred D in formula [3c]², it is singly-bound, the alkylidene of carbon number 1~10, cyclopropane ring, cyclobutane ring, ring penta Alkane ring, cyclohexane ring, cycloheptane ring, norbornene ring, adamantane ring, phenyl ring, naphthalene nucleus, tetrahydric naphthalene ring, fluorenes ring or anthracene nucleus.Its In, preferably singly-bound, the alkylidene of carbon number 1~5, cyclohexane ring or phenyl ring.

In formula [3c], D³Indicate singly-bound ,-O- ,-NH- ,-N (CH₃)-、-CONH-、-NHCO-、-COO-、-OCO-、-CON (CH₃)-or-N (CH₃)CO-、-O(CH₂)_m(integer that m is 1~5).Wherein, preferably singly-bound ,-O- ,-COO- ,-OCO- or- O(CH₂)_m(integer that m is 1~5).More preferably singly-bound ,-O- ,-OCO- or-O (CH₂)_m(integer that m is 1~5).

In formula [3c], D⁴For nitrogenous heteroaromatic, to contain at least 1 in following formula [a], formula [b] and formula [c] The heteroaromatic of a structure.

(in formula [c], Z indicates the alkylidene of carbon number 1~5).

More specifically, can enumerate pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, Quinoline ring, pyrazoline ring, isoquinolin ring, carbazole ring, purine ring, Thiadiazole, pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine Ring, triazole ring, pyridine ring, benzimidazole ring, benzimidazole ring, quinoline ring, phenanthroline ring, indole ring, quinoxaline ring, benzo thiophene Azoles ring, phenthazine ring, oxadiazoles ring or acridine ring etc. can enumerate.Wherein, preferably pyrrole ring, imidazole ring, pyrazole ring, pyridine Ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyridine ring, benzimidazole ring or benzimidazole ring.More preferably pyrrole ring, Imidazole ring, pyrazole ring, pyridine ring or pyrimidine ring.

In addition, the D in formula [3c]³It is preferred that being bonded to D⁴The not substitution adjacent with formula [a], formula [b] and formula [c] for being included Base.

In formula [3c], the integer that n is 1~4, from the perspective of the reactivity of Cong Qiyu tetracarboxylic acid sour component, preferably 1 or 2.

D in formula [3c]¹~D⁴It is D with particularly preferably combining for n¹Expression-CONH-, D²Indicate alkyl, the D of carbon number 1~5³ Indicate singly-bound, D⁴Indicate that imidazole ring or pyridine ring, n indicate 1 diamine compound.

Two amino (- NH in formula [3c]₂) bonding position do not limit.Specifically, the bonding relative to side chain Group (B¹), can enumerate 2 on phenyl ring, 3 position, 2,4 position, 2,5 position, 2,6 position, 3,4 position or 3,5 position.Wherein, reactivity when synthesizing polyamides acid, preferably 2,4 position, 2,5 position or 3,5 position.When the easiness being additionally contemplates that when synthesizing diamine compound, more preferably 2,4 position or 2,5 position.

In turn, as other diamine compounds, two aminations shown in following formula [3d-1]~formula [3d-13] also can be used It closes object and these amino is the diamine compound of secondary amino group.

(in formula [3d-1]~formula [3d-4], A¹~A⁴Each independently represent the alkylidene or fluorine-containing alkylene of carbon number 1~22 Base).

(in formula [3d-5], A¹And A³Each independently represent-COO- ,-OCO- ,-CONH- ,-NHCO- ,-CH₂-、-O-、- CO- or-NH-, A²Indicate the straight-chain of carbon number 1~22 or the straight-chain or branch of branched alkylidene or carbon number 1~22 The fluorine-containing alkylidene of shape；In formula [3d-6], A⁴And A⁶Each independently represent-COO- ,-OCO- ,-CONH- ,-NHCO- ,- CH₂,-O- ,-CO- or-NH-, A⁵Indicate the straight-chain of carbon number 1~22 or the straight chain of branched alkylidene or carbon number 1~22 Shape or branched fluorine-containing alkylidene).

(in formula [3d-7], A¹And A³Each independently represent-COO- ,-OCO- ,-CONH- ,-NHCO- ,-CH₂-、-O-、- CO- or-NH-, A²Indicate the straight-chain of carbon number 1~22 or the straight-chain or branch of branched alkylidene or carbon number 1~22 The fluorine-containing alkylidene of shape；In formula [3d-8], A⁴And A⁶Each independently represent-COO- ,-OCO- ,-CONH- ,-NHCO- ,- CH₂,-O- ,-CO- or-NH-, A⁵Indicate the straight-chain of carbon number 1~22 or the straight chain of branched alkylidene or carbon number 1~22 Shape or branched fluorine-containing alkylidene).

(in formula [3d-9], A¹And A³Each independently represent-COO- ,-OCO- ,-CONH- ,-NHCO- ,-CH2- ,-O- ,- CO- or-NH-, A²Indicate the straight-chain of carbon number 1~22 or the straight-chain or branch of branched alkylidene or carbon number 1~22 The fluorine-containing alkylidene of shape；In formula [3d-10], A⁴And A⁶Each independently represent-COO- ,-OCO- ,-CONH- ,-NHCO- ,- CH₂,-O- ,-CO- or-NH-, A⁵Indicate the straight-chain of carbon number 1~22 or the straight chain of branched alkylidene or carbon number 1~22 Shape or branched fluorine-containing alkylidene).

(in formula [3d-11], p indicates 1~10 integer).

Other diamine compounds of the invention can also be with particular polymers according to the present invention (A) and particular polymers (B) The coating of dissolubility, aligning agent for liquid crystal in a solvent, liquid crystal aligning when being made liquid crystal orientation film, voltage are kept The characteristics such as rate, accumulated charge and using a kind or mix two or more use.

It polymerize as making these polyimides systems of particular polymers of the invention (A) and particular polymers (B) i.e. The tetracarboxylic acid sour component of object is, it is preferable to use tetracarboxylic dianhydride shown in following formula [4].At this point, not only can be used shown in formula [4] Tetracarboxylic dianhydride can also use its tetracarboxylic acid derivatives, that is, tetrabasic carboxylic acid, tetracarboxylic acid acid ihalide, tetracarboxylic acid acid dialkyl ester chemical combination Tetracarboxylic dianhydride shown in formula [4] and its derivative (are also referred to as specific tetracarboxylic acid by object or tetracarboxylic acid acid dialkyl ester dihalide Sour component).

In formula [4a], Z¹~Z⁴Indicate hydrogen atom, methyl, ethyl, propyl, chlorine atom or phenyl ring, it is optionally identical each other or not Together.

In formula [4g], Z⁵And Z⁶Indicate hydrogen atom or methyl, it is optionally identical or different each other.

Among Z in formula [4], from the viewpoint of polymerisation reactivity easness when synthesizing easness, manufacture polymer, The preferably tetracarboxylic dianhydride of structure shown in formula [4a], formula [4c]~formula [4g] or formula [4k] and its tetracarboxylic acid derivatives.It is more excellent It is selected as structure shown in formula [4a] or formula [4e]~formula [4g].Particularly preferably structure shown in formula [4a], formula [4e] or formula [4f] Tetracarboxylic dianhydride and its tetracarboxylic acid derivatives.

Specific tetracarboxylic acid sour component in particular polymers (A) and particular polymers (B) of the invention whole tetrabasic carboxylic acids at Divide preferably 1 mole of %~100 mole % in 100 moles of %.Wherein, preferably 5 moles of %~95 mole %.More preferably 20 Mole %~80 mole %.

Specific tetracarboxylic acid sour component of the invention can also particular polymers (A) according to the present invention and particular polymers (B) exist The coating of dissolubility, aligning agent for liquid crystal in solvent, liquid crystal aligning when being made liquid crystal orientation film, voltage are kept The characteristics such as rate, accumulated charge and using a kind or mix two or more use.

In the polyimides based polymer of particular polymers (A) and particular polymers (B) of the invention, this hair is not being damaged In the range of obvious results fruit, other tetracarboxylic acid sour components other than specific tetracarboxylic acid sour component also can be used.

As other tetracarboxylic acid sour components, tetracarboxylic compound described below, tetracarboxylic dianhydride, tetrabasic carboxylic acid can be enumerated Dihalide, tetracarboxylic acid acid dialkyl ester compound or tetracarboxylic acid acid dialkyl ester dihalide.

That is, as other tetracarboxylic acid sour components, 1,2,5,6- naphthalene tetracarboxylic acids, Isosorbide-5-Nitrae can be enumerated, 5,8- naphthalene tetracarboxylic acids, 1,2, 5,6- anthracene tetrabasic carboxylic acid, 3,3 ', 4,4 '-biphenyltetracarboxyacid acids, 2,3,3 ', 4- biphenyltetracarboxyacid acid, bis- (3,4- dicarboxyphenyi) ethers, 3, 3 ', 4,4 '-benzophenone tetrabasic carboxylic acids, bis- (3,4- dicarboxyphenyi) sulfones, bis- (3,4- dicarboxyphenyi) methane, 2,2- it is bis- (3, 4- dicarboxyphenyi) propane, bis- (3,4- dicarboxyphenyi) propane of 1,1,1,3,3,3- hexafluoro -2,2-, bis- (3,4- dicarboxyl benzene Base) dimethylsilane, bis- (3,4- dicarboxyphenyi) diphenyl silanes, 2,3,4,5- pyridine tetrabasic carboxylic acid, bis- (the 3,4- dicarboxyls of 2,6- Base phenyl) pyridine, 3,3 ', 4,4 '-diphenyl sulfone tetrabasic carboxylic acids, 3,4,9,10- tetrabasic carboxylic acid or 1,3- diphenyl -1,2,3,4- ring Butane tetracarboxylic acid etc..

Other tetracarboxylic acid sour components of the invention can also be with particular polymers according to the present invention (A) and particular polymers (B) The coating of dissolubility, aligning agent for liquid crystal in a solvent, liquid crystal aligning when being made liquid crystal orientation film, voltage are kept The characteristics such as rate, accumulated charge and using a kind or mix two or more use.

In the present invention, for making particular polymers (A) and particular polymers (B) i.e. these polyimides based polymers Method is not particularly limited.Diamine component is reacted with tetracarboxylic acid sour component to obtain.In general, it can enumerate: make to select The derivative of free tetracarboxylic dianhydride and its tetrabasic carboxylic acid composition group at least one kind of tetracarboxylic acid sour component and include one or more The diamine component of diamine compound reacts the method for obtaining polyamic acid.Specifically, following method can be used: making tetracarboxylic acid Acid dianhydride and primary diamines compound or secondary diamine compounds polycondensation and obtain the method for polyamic acid, make tetrabasic carboxylic acid and primary diamines Close object or secondary diamine compounds dehydrating polycondensation reaction occurs and obtain the method for polyamic acid or make tetracarboxylic acid acid ihalide with Primary diamines compound or secondary diamine compounds polycondensation and the method for obtaining polyamic acid.

Following method can be used in polyamic acid Arrcostab in order to obtain: making the tetrabasic carboxylic acid for being esterified carboxylic acid group's dialkyl group With primary diamines compound or the method for secondary diamine compounds polycondensation, make the tetracarboxylic acid acid ihalide for being esterified carboxylic acid group's dialkyl group with The method of primary diamines compound or secondary diamine compounds polycondensation or the method that the carboxyl of polyamic acid is converted into ester.

Polyimides in order to obtain, can be used makes foregoing polyamides acid or polyamic acid Arrcostab closed loop and polyamides is made The method of imines.

Reacting for diamine component and tetracarboxylic acid sour component is usually that diamine component carries out in a solvent with tetracarboxylic acid sour component.As The solvent used at this time is not particularly limited as long as the solvent for dissolving polyimide precursor generated.It is following to enumerate The concrete example of the solvent used is reacted, but is not limited to these examples.

Such as n-methyl-2-pyrrolidone, N- ethyl-2-pyrrolidone or gamma-butyrolacton, N, N- dimethyl can be enumerated Formamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide or 1,3- dimethyl-imidazolinone.In addition, in polyimide precursor In the case that solvent solubility is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4- hydroxy-4-methyl-2-pentanone or following can be used Solvent shown in formula [D-1]~formula [D-3].

(in formula [D-1], D¹Indicate the alkylidene of carbon number 1~3；In formula [D-2], D²Indicate the alkylidene of carbon number 1~3；Formula In [D-3], D³Indicate the alkylidene of carbon number 1~4).

These solvents can be used alone, and can also be used in mixed way.In turn, even not dissolving the molten of polyimide precursor Agent can also be mixed and be used into aforementioned solvents in the range of polyimide precursor generated will not be precipitated.In addition, molten Moisture in agent can hinder polymerization reaction, also become the reason of hydrolyzing polyimide precursor generated, therefore solvent is preferred It is used after dehydration and drying.

When reacting diamine component in a solvent with tetracarboxylic acid sour component, the following methods can be enumerated: stirring makes diamine component Be dispersed or dissolved in solution made of solvent, directly add tetracarboxylic acid sour component or make its disperse or dissolve to solvent and add Method；Conversely, to making tetracarboxylic acid sour component be dispersed or dissolved in the method for adding diamine component in solution made of solvent；Alternately Diamine component and the method for tetracarboxylic acid sour component etc. are added, method either can be used in these.In addition, using a variety of two respectively Amine component or tetracarboxylic acid sour component and when making its reaction, can react in the state of being pre-mixed, can also respectively according to Secondary response can also be that low-molecular weight made of individually reaction is mixed reaction and polymer is made.Polymerization temperature at this time Degree can choose -20 DEG C~150 DEG C of arbitrary temp, preferably -5 DEG C~100 DEG C of range.In addition, reaction can be with any Concentration carries out, but when concentration is too low, it is difficult to obtain the polymer of high molecular weight, when excessive concentration, the viscosity of reaction solution becomes It is excessively high, be difficult to uniform stirring.It is therefore preferable that for 1~50 mass %, more preferably 5~30 mass %.Initial reaction stage is with high concentration It carries out, solvent can be added thereafter.

In the polymerization reaction of polyimide precursor, the total mole number of diamine component and the ratio between the total mole number of tetracarboxylic acid sour component Preferably 0.8~1.2.In the same manner as common polycondensation reaction, the molar ratio is closer to 1.0, then the polyimide precursor that generates Molecular weight become bigger.

Polyimides of the invention is polyimides obtained from making aforementioned polyimide precursor closed loop, the polyimides In, the closed loop rate (also referred to as acid imide rate) of amide acidic group not necessarily needs to be 100%, can depending on the application, purpose appoints Meaning adjustment.

As the method for making polyimide precursor carry out imidizate, can enumerate: the solution of polyimide precursor is straight It connects the hot-imide of heating or adds the catalysis imidizate of catalyst into the solution of polyimide precursor.

100 DEG C~400 DEG C of temperature when polyimide precursor being made to carry out hot-imide in the solution, preferably 120 DEG C~250 DEG C, it is preferred that the water generated in imidization reaction is expelled to outside system on one side, carries out hot acid imide on one side The method of change.

The catalysis imidizate of polyimide precursor can be by adding base catalysis in the solution to polyimide precursor Agent and acid anhydrides are stirred with -20 DEG C~250 DEG C, preferably with 0 DEG C~180 DEG C to carry out.The amount of basic catalyst is amide acidic group 0.5 mole times~30 moles times, preferably 2 moles times~20 moles times, the amount of acid anhydrides is 1 mole times~the 50 of amide acidic group to rub That times, preferably 3 moles times~30 moles times.As basic catalyst, pyridine, triethylamine, trimethylamine, tri-n-butylamine can be enumerated Or trioctylamine etc., wherein pyridine has the alkalinity for being suitable for promoting reaction, so it is preferred that.As acid anhydrides, can enumerate acetic anhydride, Trihemellitic acid acid anhydride or benzenetetrahydride etc., wherein when using acetic anhydride, purification after reaction is become easy, so it is preferred that. It can be controlled based on the acid imide rate of catalysis imidizate by adjusting catalytic amount and reaction temperature, reaction time.

It is sub- from polyimide precursor or polyamides generated is recycled in the reaction solution of polyimide precursor or polyimides When amine, reaction solution can be put into makes its precipitating into solvent.As the solvent for precipitating, can enumerate methanol, ethyl alcohol, Isopropanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), toluene, benzene, water etc..It puts into solvent And the polymer for precipitating it can carry out air drying or heat drying after being recovered by filtration under normal or reduced pressure.In addition, It, can when the polymer for recycling precipitating being dissolved in solvent again and carrying out the operation of reprecipitation recycling and is repeated 2 times~10 times Reduce the impurity in polymer.As the solvent at this point, it can enumerate such as alcohols, ketone or hydrocarbon, using selected from these it In 3 kinds or more solvents when, purification efficiency further increases, so it is preferred that.

Aligning agent for liquid crystal of the invention is the coating solution for being used to form liquid crystal orientation film (also referred to as resin coating), It is containing particular polymers (A), particular polymers (B) and solvent and the coating solution for being used to form liquid crystal orientation film.

Appointing in polyamic acid, polyamic acid Arrcostab and polyimides can be used in particular polymers (A) of the invention Meaning polyimides based polymer.Wherein, preferably polyamic acid Arrcostab or polyimides.More preferably polyimides.

Appointing in polyamic acid, polyamic acid Arrcostab and polyimides can be used in particular polymers (B) of the invention Meaning polyimides based polymer.Wherein, preferably polyamic acid or polyamic acid Arrcostab.More preferably polyamic acid.

About the ratio of particular polymers (A) and particular polymers (B) in aligning agent for liquid crystal of the invention, relatively In 100 mass parts of particular polymers (A), particular polymers (B) are preferably 0.5 mass parts~950 mass parts.Wherein, preferably 10 mass parts~900 mass parts, more preferably 10 mass parts~400 mass parts.

Whole component of polymer in aligning agent for liquid crystal of the invention can be particular polymers of the invention (A) With particular polymers (B), other polymer in addition to this can also be mixed with.As polymer in addition to this, can enumerate Polyimides based polymer out without the structure of the invention with tertiary N atom and the polyamides without specific structure (2) are sub- Amine system polymer.In turn, it can also enumerate cellulose-based polymer, acrylic polymer, methacrylic polymer, gather Styrene, polyamide or polysiloxanes etc..At this point, the content of other polymer in addition to this is relative to will be of the invention specific Polymer (A) and total 100 mass parts of particular polymers of particular polymers (B) are 0.5 mass parts~30 mass parts.Wherein, Preferably 1 mass parts~20 mass parts.

In addition, the solvent content in aligning agent for liquid crystal of the invention is preferably 70 mass of mass %~99.9 %.It should Content can be suitably changed according to the target film thickness of the coating method of aligning agent for liquid crystal, liquid crystal orientation film.

As long as solvent used in aligning agent for liquid crystal of the invention dissolves particular polymers (A) and particular polymers (B) solvent (also referred to as good solvent) is just not particularly limited.Following concrete examples for enumerating good solvent, but it is not limited to these Example.

For example, n,N-Dimethylformamide, n,N-dimethylacetamide, n-methyl-2-pyrrolidone, N- second can be enumerated Base -2-Pyrrolidone, dimethyl sulfoxide, gamma-butyrolacton, 1,3- dimethyl-imidazolinone, methyl ethyl ketone, cyclohexanone, cyclopentanone or 4- hydroxy-4-methyl-2-pentanone etc..

Wherein, it is preferable to use n-methyl-2-pyrrolidone, N- ethyl-2-pyrrolidone, gamma-butyrolacton.

In turn, it is preferable to use previously described formula when the dissolubility of particular polymers (A) and particular polymers (B) in a solvent is high Solvent shown in [D-1]~formula [D-3].

Good solvent in aligning agent for liquid crystal of the invention is preferably the solvent entirety for including in aligning agent for liquid crystal 20 mass of mass %~99 %.Wherein, preferably 20 mass of mass %~90 %.More preferably 30 matter of mass %~80 Measure %.

In aligning agent for liquid crystal of the invention, within the scope of the effect of the invention, can be used makes coating fluid The solvent (also referred to as poor solvent) that painting film property, the surface smoothness of liquid crystal orientation film when brilliant aligning agent improve.It is following The concrete example of poor solvent is enumerated, but is not limited to these examples.

Such as ethyl alcohol, isopropanol, n-butyl alcohol, 2- butanol, isobutanol, the tert-butyl alcohol, 1- amylalcohol, 2- amylalcohol, 3- can be enumerated Amylalcohol, 2-methyl-1-butene alcohol, isoamyl alcohol, tert-pentyl alcohol, 3- methyl -2- butanol, neopentyl alcohol, 1- hexanol, 2- methyl-1-pentene alcohol, 2- Methyl -2- amylalcohol, 2- ethyl-n-butyl alcohol, 1-heptanol, 2- enanthol, 3- enanthol, 1- octanol, sec-n-octyl alcohol, 2- ethyl -1- hexanol, ring Hexanol, 1 methyl cyclohexanol, 2 methyl cyclohexanol, 3 methyl cyclohexanol, 1,2- ethylene glycol, 1,2- propylene glycol, 1,3- propylene glycol, 1,2- butanediol, 1,3 butylene glycol, 1,4- butanediol, 2,3- butanediol, 1,5- pentanediol, 2- methyl -2,4-PD, 2- second Base -1,3- hexylene glycol, dipropyl ether, dibutyl ethers, hexyl ether, dioxanes, ethylene glycol dimethyl ether, ethylene glycol diethyl Ether, ethylene glycol dibutyl ethers, 1,2- butoxy ethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol first Benzyl ethyl ether, diethylene glycol dibutyl ether, 2 pentanone, propione, methyl-n-butyl ketone, 2-HEPTANONE, 4- heptanone, 3- ethoxybutyl acetic acid Ester, 1- methyl amyl acetic acid esters, 2- ethyl-butyl acetic acid esters, 2- ethylhexyl acetate, ethylene glycol acetate, ethylene glycol two Acetic acid esters, propylene carbonate, ethylene carbonate, 2- (methoxymethoxy) ethyl alcohol, ethylene glycol monobutyl ether, ethylene glycol list isoamyl Base ether, ethylene glycol mono hexyl ether, 2- (hexyloxy) ethyl alcohol, furfuryl alcohol, diethylene glycol, propylene glycol, glycol monobutyl ether, 1- (fourth Oxygroup ethyoxyl) propyl alcohol, propylene glycol monomethyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol list ethyl Ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, ethylene glycol single methyl ether acetic acid esters, ethylene glycol monomethyl ether acetic acid Ester, ethylene glycol monobutyl ether acetic acid esters, ethylene glycol acetate, ethylene acetate, diethylene glycol monoethyl ether acetic acid esters, Diethylene glycol monobutyl ether acetic acid esters, 2- (2- ethoxy ethoxy) ethylhexoate, diethylene glycol acetic acid esters, triethylene glycol, Triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, acetic acid are just Butyl ester, acetic acid propylene glycol monoethyl, methyl pyruvate, ethyl pyruvate, 3- methoxy methyl propionate, 3- ethoxy-propionic acid first Base ethyl ester, 3- methoxypropionate, 3- ethoxy-propionic acid, 3- methoxypropionic acid, 3- methoxy propyl propyl propionate, 3- methoxy propyl Acid butyl ester, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactate or previously described formula [D-1]~formula [D- 3] solvent shown in etc..

Wherein, it is preferable to use 1- hexanol, cyclohexanol, 1,2- ethylene glycol, 1,2-PD, glycol monobutyl ether, second two Alcohol single-butyl ether or dipropylene glycol dimethyl ether.

These poor solvents are preferably 1 mass of mass %~80 % of the solvent entirety for including in aligning agent for liquid crystal. Wherein, preferably 10 mass of mass %~80 %.More preferably 20 mass of mass %~70 %.

Following cross-linked compound is preferably imported in aligning agent for liquid crystal of the invention: there is epoxy group, isocyanates The cross-linked compound of base, oxetanyl or cyclocarbonate radical；With selected from hydroxyl, hydroxy alkyl and lower alkoxy alkane The cross-linked compound of at least one kind of substituent group in base；Alternatively, the cross-linked compound with polyunsaturated bond.These Substituent group, there are 2 or more in cross-linked compound for polyunsaturated bond needs.

As the cross-linked compound with epoxy group or isocyanate group, such as bisphenol acetone glycidol can be enumerated Ether, phenol novolac epoxy resins, cresol novolac epoxy, triglycidyl group isocyanuric acid ester, four shrinks are sweet Bis- (amino-ethyl) hexamethylenes of oil base aminobphenyl, four glycidyl group m-xylene diamine, four glycidyl group -1,3-, four benzene Base glycidol ether ethane, trisphenyl glycidyl ether ethane, bis-phenol hexafluoro acetyl group diglycidyl ether, 1,3- it is bis- (1- (2, 3- glycidoxy) -1- trifluoromethyl -2,2,2- trifluoromethyl) benzene, 4,4- bis- (2,3- glycidoxy) octafluorobiphenyls, three Glycidyl para-aminophenol, four glycidyl group m-xylene diamine, 2- (4- (2,3- glycidoxy) phenyl) -2- (4- (bis- (4- (2,3- glycidoxy) phenyl) ethyls of 1,1-) phenyl) propane or bis- (4- (1- (4- (the third oxygen of 2,3- epoxy of 1,3- Base) phenyl) -1- (4- (1- (4- (2,3- glycidoxy) phenyl) -1- Methylethyl) phenyl) ethyl) phenoxy group) -2- propyl alcohol Deng.

Cross-linked compound with oxetanyl is with oxetanes shown at least two following formula [4A] The cross-linked compound of base.

Specifically, page 58~the 59 of International Publication bulletin WO2011/132751 (2011.10.27 is disclosed) can be enumerated Cross-linked compound shown in formula [4a]~formula [4k] disclosed in page.

As the cross-linked compound with cyclocarbonate radical, for the acid of ring carbon shown at least two following formula [5A] The cross-linked compound of ester group.

Specifically, page 76~page 82 of International Publication bulletin WO2012/014898 (2012.2.2 is disclosed) can be enumerated Cross-linked compound shown in disclosed formula [5-1]~formula [5-42].

As the cross-linked compound at least one kind of substituent group in the group for selecting free hydroxyl and alkoxy to form, example The amino resins with hydroxyl or alkoxy, such as melamine resin, carbamide resin, guanamine resin, glycoluril-formaidehyde tree can such as be enumerated Rouge, succinyl amine-formaldehyde resin or ethylene urea-formaldehyde resins etc..Specifically, the hydrogen atom of amino can be used by methylol Or melamine derivative, benzoguanamine derivative or glycoluril made of alkoxy methyl or the two substitution.The melamine derivative Or benzoguanamine derivative can exist in the form of dimer or tripolymer.Their preferably every 1 triazine rings have 3 average Above and 6 methylols or alkoxy methyl below.

As this melamine derivative or the example of benzoguanamine derivative, every 1 triazine ring of commercially available product can be enumerated The MX-750 for there are average 3.7 methoxies, every 1 triazine ring is replaced to replace the MW-30 for there are average 5.8 methoxies (the above are Sanwa Chemical Co., Ltd's systems), the first such as CYMEL 300,301,303,350,370,771,325,327,703,712 Oxygroup methylation melamine；The methoxymethylated butoxymethyl melamine such as CYMEL 235,236,238,212,253,254； The butoxymethyls melamines such as CYMEL 506,508；The carboxylic methoxymethylated isobutoxy of CYMEL 1141 etc Methylate melamine；The methoxymethylated ethoxyl methyl benzoguanamine of CYMEL 1123 etc；CYMEL 1123-10 etc Methoxymethylated butoxymethyl benzoguanamine；The butoxymethyl benzoguanamine of CYMEL 1128 etc；CYMEL (the above are three well サイア Na ミ De are public for the carboxylic methoxymethylated ethoxyl methyl benzoguanamine of 1125-80 etc Department's system).In addition, the example as glycoluril, can enumerate butoxymethyl glycoluril, the CYMEL 1172 of CYMEL 1170 etc Etc methylolation glycoluril etc., the methoxyl group methylolation glycoluril of Powder link 1174 etc etc..

As benzene or benzene phenoloid with hydroxyl or alkoxy, such as 1,3,5- tri- (methoxy methyls can be enumerated Base) benzene, 1,2,4- tri- (i-propoxymethyl) benzene, bis- (sec-butoxymethyl) benzene of 1,4- or 2,6- bishydroxymethyl be to tert-butyl Phenol etc..

More specifically, can enumerate page 62 of International Publication bulletin WO2011/132751 (2011.10.27 is disclosed)~ Disclosed in page 66, cross-linked compound shown in formula [6-1]~formula [6-48].

As the cross-linked compound with polyunsaturated bond, such as trimethylolpropane tris (methyl) can be enumerated Acrylate, pentaerythrite three (methyl) acrylate, dipentaerythritol five (methyl) acrylate, three (methyl) acryloyl-oxies The intramoleculars such as base oxethyl trimethylolpropane or poly- (methyl) acrylate of glycerine polyglycidyl ether have 3 polymerisms not The cross-linked compound of saturated group；In turn, ethylene glycol two (methyl) acrylate, diethylene glycol two (methyl) acrylate, Tetraethylene glycol two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, propylene glycol two (methyl) acrylate, poly- third Glycol two (methyl) acrylate, butanediol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, ethylene oxide Bisphenol A-type two (methyl) acrylate, propylene oxide bisphenol type two (methyl) acrylate, 1,6-HD two (methyl) propylene Acid esters, glycerol two (methyl) acrylate, pentaerythrite two (methyl) acrylate, ethylene glycol diglycidylether two (methyl) Acrylate, diethylene glycol diglycidyl glycerin ether two (methyl) acrylate, o-phthalic acid diglycidyl ester two (methyl) The intramoleculars such as acrylate or 3-hydroxypivalic acid neopentyl glycol two (methyl) acrylate have 2 polymerism unsaturated groups Cross-linked compound；And (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 2- hydroxy propyl ester, (methyl) acrylic acid 2- hydroxybutyl, 2- phenoxy group -2- hydroxypropyl (methyl) acrylate, 2- (methyl) acryloxy -2- hydroxypropyl are adjacent Phthalic acid ester, 3- chlorine-2-hydroxyl propyl (methyl) acrylate, glycerol list (methyl) acrylate, 2- (methyl) acryloyl The intramoleculars such as oxygroup ethyl phosphonic acid ester or N- methylol (methyl) acrylamide have the bridging property of 1 polymerism unsaturated group Compound etc..

Also, following formula [7A] compound represented also can be used.

(in formula [7A], E¹It indicates to be selected from cyclohexane ring, bis cyclohexane ring, phenyl ring, cyclohexyl biphenyl, terphenyl ring, naphthalene nucleus, fluorenes It is at least one kind of in ring, anthracene nucleus and phenanthrene ring, E²Indicate the group in following formula [7a] or formula [7b], n indicate 1~4 it is whole Number).

Above compound is an example of cross-linked compound, but is not limited to them.In addition, at liquid crystal aligning of the invention Cross-linked compound used in reason agent can be a kind, can also combine two or more.

The content of cross-linked compound in aligning agent for liquid crystal of the invention is relative to whole 100 matter of component of polymer Measuring part is preferably 0.1 mass parts~150 mass parts.Wherein, target effect is shown in order to promote cross-linking reaction, relative to Whole 100 mass parts of component of polymer, preferably 0.1 mass parts~100 mass parts.More preferably 1 mass parts~50 mass parts.

In aligning agent for liquid crystal of the invention, within the scope of the effect of the invention, can be used makes coating fluid The compound that film thickness uniformity, the surface smoothness of liquid crystal orientation film when brilliant aligning agent improve.

As the compound for improving the film thickness uniformity of liquid crystal orientation film, surface smoothness, fluorine system surface can be enumerated Activating agent, silicone based surfactants, nonionic surfactants etc..

More specifically, for example, can enumerate Eftop EF301, EF303, EF352 (more than, Tohkem products Corporation system)；Megafac F171, F173, R-30 (more than, big Japanese ink Co. Ltd. system)；Fluorad FC430, FC431 (more than, Sumitomo 3M Limited system)；AsahiGuard AG710,Surflon S-382,SC101, SC102, SC103, SC104, SC105, SC106 (more than, Asahi Glass Co., Ltd's system) etc..

The use ratio of these surfactants is relative to the whole component of polymer 100 contained in aligning agent for liquid crystal Mass parts are preferably 0.01 mass parts~2 mass parts, more preferably 0.01 mass parts~1 mass parts.

In turn, in aligning agent for liquid crystal of the invention, as the charge movement promoted in liquid crystal orientation film, promote element The compound of de- charge, can also add page 69~the 73 of International Publication bulletin WO2011/132751 (2011.10.27 is disclosed) Nitrogen-containing heterocycle amine compounds shown in disclosed in page, formula [M1]~formula [M156].The amine compounds can be added directly to liquid In brilliant aligning agent, it is 0.1 mass of mass %~10 %, preferably 1 mass %~7 that concentration preferably, which is made, with solvent appropriate It is added again after the solution of quality %.As the solvent, as long as dissolving above-mentioned particular polymers (A) and particular polymers (B) Solvent is just not particularly limited.

In aligning agent for liquid crystal of the invention, in addition to above-mentioned poor solvent, cross-linked compound, make resin coating or liquid The compound and promote to take off except the compound of charge that film thickness uniformity, the surface smoothness of brilliant alignment films improve, as long as It does not damage in the range of effect of the present invention, then can also add the electricity such as dielectric constant, the electric conductivity for changing liquid crystal orientation film Dielectric substance, the conductive materials of characteristic.

After aligning agent for liquid crystal of the invention can be coated on substrate and be burnt into, brushing processing, light irradiation etc. are utilized Orientation process is carried out, so as to be used as liquid crystal orientation film.In addition, in the case wheres vertically oriented purposes etc., without orientation Processing can also act as liquid crystal orientation film.As the substrate used at this time, do not limited especially as long as the high substrate of the transparency It is fixed, other than glass substrate, plastic bases such as acrylic compounds substrate, polycarbonate substrate etc. can also be used.It conforms to the principle of simplicity chemical industry , it is preferable to use being formed with the substrate of ITO electrode for driving liquid crystal etc. from the perspective of skill.In addition, the liquid of reflection-type is made When crystalline substance indicates element, if being only unilateral substrate, the opaque substrate such as silicon wafer also can be used, as electrode at this time, Also the material of the meeting reflected light such as aluminium can be used.

The coating method of aligning agent for liquid crystal is not particularly limited, and industrial is usually to utilize silk-screen printing, graph The method of the progress such as brush, flexible printing or ink-jet method.As other coating methods, have infusion process, rolling method, slot coated method, Spin-coating method or spray coating method etc. can use these methods according to purpose.

After aligning agent for liquid crystal is coated on substrate, dried using hot plate, thermal cycle type baking oven or IR (infrared ray) type The heating meanss such as case, the solvent according to used in aligning agent for liquid crystal, with 30~300 DEG C, preferably with 30~250 DEG C of temperature Evaporate solvent, so as to which liquid crystal orientation film is made.When the thickness of liquid crystal orientation film after firing is blocked up, member is indicated in liquid crystal Be in terms of the power consumption of part it is unfavorable, when thickness is excessively thin, liquid crystal indicates that the reliability of element reduces sometimes, therefore preferably 5~ 300nm, more preferably 10~100nm.When making liquid crystal horizontal alignment, tilted alignment, irradiated by brushing or polarized UV rays etc. Liquid crystal orientation film after firing is handled.

Element is indicated about liquid crystal of the invention, and band liquid is obtained by aligning agent for liquid crystal of the invention by the above method After the substrate of brilliant alignment films, liquid crystal cells are made using known method, so that liquid crystal, which is made, indicates element.

As the production method of liquid crystal cells, following method can be exemplified: preparing a pair of of the base for being formed with liquid crystal orientation film Plate spreads spacer on the liquid crystal orientation film of a substrate, is pasted in such a way that the surface of liquid crystal orientation film is towards inside The method that another substrate injection liquid crystal at decompression and is sealed；Alternatively, being added dropwise to the liquid crystal alignment film surface for being scattered with spacer After liquid crystal, adhesive substrates and the method etc. being sealed.

In turn, aligning agent for liquid crystal of the invention is also preferably used for having liquid crystal between a pair of of the substrate for having electrode Layer and the liquid crystal manufactured via following process expression element: liquid-crystal composition, the liquid crystal combination are configured between a pair of of substrate Object includes the polymerizable compound polymerizeing by least one of active energy beam and heat, while to voltage is applied between electrode Side polymerize polymerizable compound by least one of irradiation active energy beam and heating.Herein, as active energy Ray is measured, ultraviolet light is suitably for.As ultraviolet light, wavelength is 300~400nm, preferably 310~360nm.It is carried out using heating When polymerization, heating temperature is 40~120 DEG C, preferably 60~80 DEG C.Furthermore it is possible to carry out ultraviolet light and heating simultaneously.

Above-mentioned liquid crystal indicates that element passes through the side PSA (polymer stabilizing orientation, Polymer Sustained Alignment) Formula controls the pre-tilt angle of liquid crystal molecule.In PSA mode, be mixed into liquid crystal material in advance a small amount of photopolymerizable compound, Such as photopolymerization monomer, after assembling liquid crystal cells, in the state of applying specific voltage to liquid crystal layer, to optical polymerism chemical combination Object irradiates ultraviolet light etc., and the pre-tilt angle of liquid crystal molecule is controlled by polymer generated.Generate the liquid crystal point when polymer The state of orientation of son is also remembered after removing voltage, therefore the electric field etc. by being formed in control liquid crystal layer, can adjust liquid The pre-tilt angle of brilliant molecule.In addition, without carrying out brushing processing in PSA mode, thus suitably form be difficult to by brushing processing come Control the vertical alignment-type liquid crystal layer of pre-tilt angle.

That is, indicating element about liquid crystal of the invention, obtained using the above method by aligning agent for liquid crystal of the invention After substrate with liquid crystal orientation film, liquid crystal cells are made, polymerism is made by least one of irradiation ultraviolet light and heating Compound polymerization, so as to control the orientation of liquid crystal molecule.

If enumerating an example of the liquid crystal cells of production PSA mode, can enumerate: preparation is formed with liquid crystal orientation film A pair of of substrate spreads spacer on the liquid crystal orientation film of a substrate, pastes in such a way that liquid crystal orientation film is facing towards inside In the method that another substrate, decompression inject liquid crystal and be sealed；Alternatively, in the liquid crystal alignment film surface for being scattered with spacer After liquid crystal is added dropwise, adhesive substrate and the method etc. being sealed.

The polymerizable compound polymerizeing by heat, ultraviolet light irradiation is mixed in liquid crystal.As polymerizable compound, can arrange Enumerate compound of the intramolecular with polymerisms unsaturated groups such as 1 or more acrylate-based, methacrylates.This When, polymerizable compound is preferably 0.01~10 mass parts relative to 100 mass parts of liquid crystal composition, more preferably 0.1~5 mass Part.When polymerizable compound is less than 0.01 mass parts, polymerizable compound will not polymerize and be unable to control the orientation of liquid crystal, be more than When 10 mass parts, unreacted polymerizable compound, which becomes after image characteristic more, that liquid crystal indicates element, to be reduced.

Make liquid crystal cells after, on one side to liquid crystal cells apply AC or DC voltage, heat on one side, irradiate it is ultraviolet Line, so that polymerizable compound be made to polymerize.Thus, it is possible to control the orientation of liquid crystal molecule.

In turn, aligning agent for liquid crystal of the invention is also preferably used for having liquid crystal between a pair of of the substrate for having electrode Layer and the liquid crystal manufactured via following process expression element, i.e. SC-PVA mode: configuration liquid crystal takes between aforementioned a pair of of substrate To film, the liquid crystal orientation film includes the polymerizable group polymerizeing by least one of active energy beam and heat, in electricity Apply voltage between pole.Herein, as active energy beam, it is suitably for ultraviolet light.As ultraviolet light, wavelength is 300~ 400nm, preferably 310~360nm.When being polymerize using heating, heating temperature is 40~120 DEG C, preferably 60~80 DEG C. Furthermore it is possible to apply ultraviolet light and heating simultaneously.

It is taken to obtain the liquid crystal of the polymerizable group comprising polymerizeing by least one of active energy beam and heat To film, the following methods can be enumerated: the compound comprising the polymerizable group is added the method in aligning agent for liquid crystal； Use the method for the component of polymer comprising polymerizable group.

If enumerating an example of the liquid crystal cells of production SC-PVA mode, can enumerate: preparation is formed with of the invention A pair of of substrate of liquid crystal orientation film, spreads spacer on the liquid crystal orientation film of a substrate, with liquid crystal orientation film facing towards interior The mode of side is pasted on another substrate, the method that decompression is injected liquid crystal and is sealed；Alternatively, in the liquid for being scattered with spacer After liquid crystal is added dropwise on crystalline substance orientation film surface, adhesive substrate and the method etc. being sealed.

After making liquid crystal cells, while liquid crystal cells are applied with the voltage of AC or DC, Bian Jiare, irradiation ultraviolet light, from And the orientation of liquid crystal molecule can be controlled.

As above operation, aligning agent for liquid crystal of the invention can obtain after long-time is exposed to high temperature and light irradiation Also it can express and to stablize the liquid crystal orientation film of pre-tilt angle.Also, electricity can be inhibited long-time is exposed to after light irradiation by being formed The liquid crystal orientation film that the reduction of pressure conservation rate and the residual charge accumulated by DC voltage quickly mitigate.Thus, have by this The liquid crystal for the liquid crystal orientation film that the aligning agent for liquid crystal of invention obtains indicates the excellent in reliability of element, can be suitably employed in big Picture and the LCD TV of high-resolution, middle-size and small-size auto-navigation system, smart phone etc..

Embodiment

Being exemplified below embodiment, present invention be described in more detail, but is not limited to them.

" used in synthesis example of the invention, embodiment and comparative example referred to as "

Using referred to as follows in synthesis example, embodiment and comparative example.

(specific diamine compound (1) of the invention)

A1: diamine compound shown in following formula [A1]

A2: diamine compound shown in following formula [A2]

A3: diamine compound shown in following formula [A3]

(specific diamine compound (2) of the invention)

B1: diamine compound shown in following formula [B1]

(specific side chain type diamine compound of the invention)

C1:1,3- diamino -4- (4- (trans- -4- n-heptyl cyclohexyl) phenoxy group) benzene

C2:1,3- diamino -4- (4- (trans- -4- n-heptyl cyclohexyl) phenoxymethyl) benzene

C3:1,3- diamino -4- { 4- (trans- -4- (trans- -4- pentyl cyclohexyl) cyclohexyl) phenoxy group } benzene

C4: diamine compound shown in following formula [C4]

(other diamine compounds)

D1: p-phenylenediamine

D2:3,5- diaminobenzoic acid

D3:1,3- diamino -4- octadecane epoxide benzene

(specific tetracarboxylic acid sour component of the invention)

E1:1,2,3,4- cyclobutane tetracarboxylic dianhydride

E2: bicyclic [3,3,0] octane -2,4,6,8- tetracarboxylic dianhydride

E3: tetracarboxylic dianhydride shown in following formula [E3]

E4: tetracarboxylic dianhydride shown in following formula [E4]

E5: tetracarboxylic dianhydride shown in following formula [E5]

" cross-linked compound used in the present invention "

K1: cross-linked compound shown in following formula [K1]

NMP:N- N-methyl-2-2-pyrrolidone N

NEP:N- ethyl-2-pyrrolidone

γ-BL: gamma-butyrolacton

BCS: ethylene glycol monobutyl ether

PB: glycol monobutyl ether

EC: diethylene glycol monoethyl ether

DME: dipropylene glycol dimethyl ether

" measurement of the molecular weight of polyimides based polymer of the invention "

About the molecular weight of polyimide precursor and polyimides in synthesis example, room temperature gel permeation chromatography is used (GPC) device (GPC-101) (Showa Denko K. K's system), column (KD-803, KD-805) (Shodex corporation), it is following to grasp Make to measure.

Column temperature: 50 DEG C

Eluent: N, N '-dimethyl formamide is (as additive, lithium bromide monohydrate (LiBrH₂O) it is 30mmol/L (liter), phosphoric acid anhydrous crystal (orthophosphoric acid) are 30mmol/L, tetrahydrofuran (THF) is 10ml/L)

Flow velocity: 1.0ml/ minutes

About 900,000,150,000 standard curve making standard sample: TSK standard polyethylene oxide (molecular weight:, 100,000 and 30,000) (TOSOH Co., Ltd's system) and polyethylene glycol (molecular weight: about 12,000,4,000 and 1,000) (Polymer Laboratories Ltd. system).

" measurement of the acid imide rate of polyimides of the invention "

The acid imide rate of polyimides in synthesis example is operated as follows to measure.By polyimide powder 20mg put into NMR (nuclear magnetic resonance) sample cell (NMR sample cell specification, φ 5 (wasteland's science Co. Ltd. system)) adds deuterated dimethyl sulfoxide (DMSO-d6,0.05 mass %TMS (tetramethylsilane) melange) (0.53ml), is made it completely dissolved with ultrasonic wave.It utilizes Proton NMR of the NMR measuring machine (JNW-ECA500) (JEOL DATUM corporation) to solution measurement 500MHz.Acid imide rate The proton for being originated from the not changed structure in imidizate front and back is determined as reference proton, uses the peak integrating of the proton Value and the proton peak integrating value of the NH base from 9.5ppm~10.0ppm amic acid nearby occurred are found out using the following formula.

Acid imide rate (%)=(1- α x/y) × 100

In above-mentioned formula, x is the proton peak integrating value of the NH base from amic acid, the peak integrating value that y is benchmark proton, α are NH matrix son 1 number ratio of the reference proton relative to amic acid when polyamic acid (acid imide rate is 0%).

" synthesis of polyimides based polymer of the invention "

In the NMP (25.5g) mixing E1 (4.50g, 23.0mmol), A1 (1.85g, 9.30mmol), C1 (0.88g, It 2.32mmol) with D1 (1.26g, 11.6mmol), is reacted 8 hours with 40 DEG C, so that obtaining resin solid content concentration is 25 matter Measure the polyamic acid solution (1) of %.The number-average molecular weight of the polyamic acid is 24,200, weight average molecular weight 86,500.

In the NMP (26.1g) mixing E1 (4.10g, 20.9mmol), B1 (3.16g, 10.6mmol), D1 (0.46g, It 4.24mmol) with D2 (0.97g, 6.35mmol), is reacted 8 hours with 40 DEG C, so that obtaining resin solid content concentration is 25 matter Measure the polyamic acid solution (2) of %.The number-average molecular weight of the polyamic acid is 25,200, weight average molecular weight 89,100.

In the NEP (32.1g) mixing E2 (3.96g, 15.8mmol), A1 (1.91g, 9.61mmol), C1 (6.09g, 16.0mmol) with D2 (0.97g, 6.41mmol), after reacting 5 hours with 80 DEG C, E1 (3.10g, 15.8mmol) and NEP are added (16.0g) is reacted 6 hours with 40 DEG C, to obtain the polyamic acid solution (3) that resin solid content concentration is 25 mass %. The number-average molecular weight of the polyamic acid is 20,100, weight average molecular weight 64,100.

6 are diluted to addition NEP in the polyamic acid solution (3) (30.0g) that the synthetic method using synthesis example 3 obtains After quality %, acetic anhydride (3.45g) and pyridine (2.50g) are added as imidization catalyst, are reacted 2 hours with 60 DEG C. The reaction solution is put into methanol (460ml), and leaching gained sediment.The sediment is cleaned with methanol, with 100 DEG C are dried under reduced pressure and obtain polyimide powder (4).The acid imide rate of the polyimides is 55%, the equal molecule of number Amount is 18,500, weight average molecular weight 49,300.

In the NEP (33.4g) mixing E2 (4.47g, 17.9mmol), B1 (3.24g, 10.9mmol), C1 (2.75g, 7.23mmol) with D2 (2.75g, 18.1mmol), after reacting 5 hours with 80 DEG C, E1 (3.50g, 17.9mmol) and NEP are added (16.7g) is reacted 6 hours with 40 DEG C, to obtain the polyamic acid solution (5) that resin solid content concentration is 25 mass %. The number-average molecular weight of the polyamic acid is 22,100, weight average molecular weight 68,500.

6 are diluted to addition NEP in the polyamic acid solution (5) (30.0g) that the synthetic method using synthesis example 5 obtains After quality %, acetic anhydride (3.40g) and pyridine (2.65g) are added as imidization catalyst, are reacted 2 hours with 60 DEG C. The reaction solution is put into methanol (460ml), and leaching gained sediment.The sediment is cleaned with methanol, with 100 DEG C are dried under reduced pressure and obtain polyimide powder (6).The acid imide rate of the polyimides is 58%, the equal molecule of number Amount is 19,800, weight average molecular weight 52,900.

In the NMP (17.4g) mixing E2 (1.37g, 5.46mmol), A2 (1.18g, 5.53mmol), C2 (2.91g, 7.38mmol), D1 (0.20g, 1.84mmol) and D2 (0.56g, 3.69mmol) after reacting 5 hours with 80 DEG C, adds E1 (2.50g, 12.8mmol) and NMP (8.72g) is reacted 6 hours with 40 DEG C, so that obtaining resin solid content concentration is 25 matter Measure the polyamic acid solution of %.

After being diluted to 6 mass % to addition NMP in gained polyamic acid solution (30.0g), it is catalyzed as imidizate Agent and add acetic anhydride (4.45g) and pyridine (3.30g), with 80 DEG C react 3 hours.The reaction solution is put into methanol In (460ml), and leaching gained sediment.The sediment is cleaned with methanol, is dried under reduced pressure and is obtained with 100 DEG C Polyimide powder (7).The acid imide rate of the polyimides is 80%, and number-average molecular weight 17,100, weight average molecular weight are 47,800。

In the NMP (16.0g) mixing E2 (1.37g, 5.46mmol), B1 (1.38g, 4.61mmol), C2 (1.09g, 2.77mmol) with D2 (1.68g, 11.1mmol), after reacting 5 hours with 80 DEG C, E1 (2.50g, 12.8mmol) and NMP are added (8.02g) is reacted 6 hours with 40 DEG C, to obtain the polyamic acid solution that resin solid content concentration is 25 mass %.

After being diluted to 6 mass % to addition NMP in gained polyamic acid solution (30.0g), it is catalyzed as imidizate Agent and add acetic anhydride (4.50g) and pyridine (3.35g), with 80 DEG C react 3.5 hours.The reaction solution is put into methanol In (460ml), and leaching gained sediment.The sediment is cleaned with methanol, is dried under reduced pressure and is obtained with 100 DEG C Polyimide powder (8).The acid imide rate of the polyimides is 81%, and number-average molecular weight 18,800, weight average molecular weight are 49,800。

In the NEP (48.3g) mixing E3 (7.20g, 32.1mmol), A2 (2.78g, 13.0mmol), C2 (5.14g, It 13.0mmol) with D2 (0.99g, 6.51mmol), is reacted 8 hours with 40 DEG C, so that obtaining resin solid content concentration is 25 matter Measure the polyamic acid solution (9) of %.The number-average molecular weight of the polyamic acid is 21,200, weight average molecular weight 65,400.

6 are diluted to addition NEP in the polyamic acid solution (9) (30.0g) that the synthetic method using synthesis example 9 obtains After quality %, acetic anhydride (3.40g) and pyridine (2.63g) are added as imidization catalyst, are reacted 2 hours with 60 DEG C. The reaction solution is put into methanol (460ml), and leaching gained sediment.The sediment is cleaned with methanol, with 100 DEG C are dried under reduced pressure and obtain polyimide powder (10).The acid imide rate of the polyimides is 57%, the equal molecule of number Amount is 18,200, weight average molecular weight 48,300.

In the NMP (24.3g) mixing E3 (3.85g, 17.2mmol), A3 (0.53g, 2.61mmol), C4 (2.14g, It 4.35mmol) with D2 (1.59g, 10.4mmol), is reacted 8 hours with 40 DEG C, so that obtaining resin solid content concentration is 25 matter Measure the polyamic acid solution of %.

After being diluted to 6 mass % to addition NMP in gained polyamic acid solution (30.0g), it is catalyzed as imidizate Agent and add acetic anhydride (3.90g) and pyridine (2.65g), with 60 DEG C react 3.5 hours.The reaction solution is put into methanol In (460ml), and leaching gained sediment.The sediment is cleaned with methanol, is dried under reduced pressure and is obtained with 100 DEG C Polyimide powder (11).The acid imide rate of the polyimides is 68%, and number-average molecular weight 17,500, weight average molecular weight are 47,900。

In the NMP (17.0g) mixing E4 (1.64g, 5.46mmol), B1 (1.65g, 5.53mmol), C1 (1.40g, 3.69mmol), D1 (0.20g, 1.84mmol) and D2 (1.12g, 7.38mmol) after reacting 6 hours with 80 DEG C, adds E1 (2.50g, 12.8mmol) and NMP (8.52g) is reacted 6 hours with 40 DEG C, so that obtaining resin solid content concentration is 25 matter Measure the polyamic acid solution of %.

After being diluted to 6 mass % to addition NMP in gained polyamic acid solution (30.0g), it is catalyzed as imidizate Agent and add acetic anhydride (4.15g) and pyridine (2.95g), with 70 DEG C react 3 hours.The reaction solution is put into methanol In (460ml), and leaching gained sediment.The sediment is cleaned with methanol, is dried under reduced pressure and is obtained with 100 DEG C Polyimide powder (12).The acid imide rate of the polyimides is 64%, and number-average molecular weight 18,100, weight average molecular weight are 49,600。

In the NEP (16.6g) mixing E4 (2.87g, 9.56mmol), A3 (0.98g, 4.84mmol), C3 (2.44g, 5.65mmol), D1 (0.26g, 2.42mmol) and D2 (0.49g, 3.23mmol) after reacting 6 hours with 80 DEG C, adds E1 (1.25g, 6.37mmol) and NEP (8.30g) is reacted 6 hours with 40 DEG C, so that obtaining resin solid content concentration is 25 matter Measure the polyamic acid solution of %.

After being diluted to 6 mass % to addition NEP in gained polyamic acid solution (30.0g), it is catalyzed as imidizate Agent and add acetic anhydride (4.55g) and pyridine (3.35g), with 80 DEG C react 3 hours.The reaction solution is put into methanol In (460ml), and leaching gained sediment.The sediment is cleaned with methanol, is dried under reduced pressure and is obtained with 100 DEG C Polyimide powder (13).The acid imide rate of the polyimides is 81%, and number-average molecular weight 16,300, weight average molecular weight are 45,100。

In the NMP (17.4g) mixing E4 (3.57g, 11.9mmol), A1 (1.37g, 6.89mmol), C4 (1.70g, 3.44mmol) with D2 (1.05g, 6.89mmol), after reacting 6 hours with 80 DEG C, E1 (1.00g, 5.10mmol) and NMP are added (8.69g) is reacted 6 hours with 40 DEG C, to obtain the polyamic acid solution that resin solid content concentration is 25 mass %.

After being diluted to 6 mass % to addition NEP in gained polyamic acid solution (30.0g), it is catalyzed as imidizate Agent and add acetic anhydride (3.75g) and pyridine (2.35g), with 80 DEG C react 3 hours.The reaction solution is put into methanol In (460ml), and leaching gained sediment.The sediment is cleaned with methanol, is dried under reduced pressure and is obtained with 100 DEG C Polyimide powder (14).The acid imide rate of the polyimides is 53%, and number-average molecular weight 17,800, weight average molecular weight are 48,900。

In the NMP (17.3g) mixing E2 (1.73g, 6.91mmol), A1 (0.70g, 3.50mmol), A2 (0.75g, 3.50mmol), C2 (2.76g, 7.00mmol) and D2 (0.53g, 3.50mmol), after reacting 6 hours with 80 DEG C, add E5 (2.20g, 10.4mmol) and NMP (8.67g) is reacted 6 hours with 80 DEG C, so that obtaining resin solid content concentration is 25 matter Measure the polyamic acid solution (15) of %.The number-average molecular weight of the polyamic acid is 20,100, weight average molecular weight 62,600.

In the NMP (16.4g) mixing E2 (0.88g, 3.54mmol), B1 (1.60g, 5.37mmol), C1 (1.36g, 3.58mmol) with D2 (1.36g, 8.95mmol), after reacting 6 hours with 80 DEG C, E5 (3.00g, 14.1mmol) and NMP are added (8.21g) is reacted 6 hours with 80 DEG C, to obtain the polyamic acid solution (16) that resin solid content concentration is 25 mass %. The number-average molecular weight of the polyamic acid is 21,600, weight average molecular weight 65,100.

It is diluted to addition NMP in the polyamic acid solution (16) (30.0g) that the synthetic method using synthesis example 16 obtains To 6 mass %, acetic anhydride (4.50g) and pyridine (3.30g) are added as imidization catalyst, it is small with 80 DEG C of reactions 3 When.The reaction solution is put into methanol (460ml), and leaching gained sediment.The sediment is cleaned with methanol, It is dried under reduced pressure with 100 DEG C and obtains polyimide powder (17).The acid imide rate of the polyimides is 81%, and number is divided equally Son amount is 18,800, weight average molecular weight 52,200.

In the NEP (17.1g) mixing E2 (1.73g, 6.91mmol), A3 (0.89g, 4.38mmol), C3 (2.65g, 6.13mmol) with D2 (1.07g, 7.00mmol), after reacting 6 hours with 80 DEG C, E5 (2.20g, 10.4mmol) and NEP are added (8.54g) is reacted 6 hours with 80 DEG C, to obtain the polyamic acid solution that resin solid content concentration is 25 mass %.

After being diluted to 6 mass % to addition NMP in gained polyamic acid solution (30.0g), it is catalyzed as imidizate Agent and add acetic anhydride (4.10g) and pyridine (3.05g), with 70 DEG C react 2.5 hours.The reaction solution is put into methanol In (460ml), and leaching gained sediment.The sediment is cleaned with methanol, is dried under reduced pressure and is obtained with 100 DEG C Polyimide powder (18).The acid imide rate of the polyimides is 74%, and number-average molecular weight 17,900, weight average molecular weight are 48,300。

In the NMP (16.4g) mixing E2 (0.80g, 3.18mmol), A1 (0.96g, 4.83mmol), C1 (3.37g, 8.86mmol) with D2 (0.37g, 2.42mmol), after reacting 6 hours with 80 DEG C, E5 (2.70g, 12.7mmol) and NMP are added (8.20g) is reacted 6 hours with 80 DEG C, to obtain the polyamic acid solution that resin solid content concentration is 25 mass %.

After being diluted to 6 mass % to addition NMP in gained polyamic acid solution (30.0g), it is catalyzed as imidizate Agent and add acetic anhydride (3.75g) and pyridine (2.55g), with 60 DEG C react 2 hours.The reaction solution is put into methanol In (460ml), and leaching gained sediment.The sediment is cleaned with methanol, is dried under reduced pressure and is obtained with 100 DEG C Polyimide powder (19).The acid imide rate of the polyimides is 55%, and number-average molecular weight 16,800, weight average molecular weight are 46,200。

In the NMP (25.5g) mixing E1 (5.00g, 25.5mmol), C1 (0.98g, 2.58mmol) and D1 (2.51g, 23.2mmol), it is reacted 8 hours with 40 DEG C, to obtain the polyamic acid solution that resin solid content concentration is 25 mass % (20).The number-average molecular weight of the polyamic acid is 25,800, weight average molecular weight 88,900.

In the NMP (24.4g) mixing E1 (5.00g, 25.5mmol), D1 (1.96g, 18.1mmol) and D2 (1.18g, 7.75mmol), it is reacted 8 hours with 40 DEG C, to obtain the polyamic acid solution that resin solid content concentration is 25 mass % (21).The number-average molecular weight of the polyamic acid is 27,100, weight average molecular weight 90,100.

In the NEP (31.3g) mixing E2 (4.08g, 16.3mmol), C1 (6.29g, 16.5mmol), D1 (1.07g, 9.92mmol) with D2 (1.01g, 6.61mmol), after reacting 5 hours with 80 DEG C, E1 (3.20g, 16.3mmol) and NEP are added (15.7g) is reacted 6 hours with 40 DEG C, to obtain the polyamic acid solution (22) that resin solid content concentration is 25 mass %. The number-average molecular weight of the polyamic acid is 22,500, weight average molecular weight 66,900.

It is diluted to addition NEP in the polyamic acid solution (22) (30.0g) that the synthetic method using synthesis example 22 obtains To 6 mass %, acetic anhydride (3.40g) and pyridine (2.50g) are added as imidization catalyst, it is small with 60 DEG C of reactions 2 When.The reaction solution is put into methanol (460ml), and leaching gained sediment.The sediment is cleaned with methanol, It is dried under reduced pressure with 100 DEG C and obtains polyimide powder (23).The acid imide rate of the polyimides is 55%, and number is divided equally Son amount is 19,200, weight average molecular weight 50,600.

In the NEP (31.0g) mixing E2 (4.72g, 18.9mmol), C1 (2.91g, 7.64mmol), D1 (1.24g, 11.5mmol) with D2 (2.91g, 19.1mmol), after reacting 5 hours with 80 DEG C, E1 (3.70g, 18.9mmol) and NEP are added (15.5g) is reacted 6 hours with 40 DEG C, to obtain the polyamic acid solution (24) that resin solid content concentration is 25 mass %. The number-average molecular weight of the polyamic acid is 23,000, weight average molecular weight 68,800.

It is diluted to addition NEP in the polyamic acid solution (24) (30.0g) that the synthetic method using synthesis example 24 obtains To 6 mass %, acetic anhydride (3.40g) and pyridine (2.65g) are added as imidization catalyst, it is small with 60 DEG C of reactions 2 When.The reaction solution is put into methanol (460ml), and leaching gained sediment.The sediment is cleaned with methanol, It is dried under reduced pressure with 100 DEG C and obtains polyimide powder (25).The acid imide rate of the polyimides is 57%, and number is divided equally Son amount is 20,100, weight average molecular weight 54,100.

In the NEP (16.5g) mixing E2 (2.04g, 8.16mmol), A1 (0.99g, 4.96mmol), D2 (0.50g, 3.31mmol) with D3 (3.11g, 8.26mmol), after reacting 5 hours with 80 DEG C, E1 (1.60g, 8.16mmol) and NEP are added (8.25g) is reacted 6 hours with 40 DEG C, to obtain the polyamic acid solution that resin solid content concentration is 25 mass %.

After being diluted to 6 mass % to addition NEP in gained polyamic acid solution (30.0g), it is catalyzed as imidizate Agent and add acetic anhydride (3.45g) and pyridine (2.65g), with 60 DEG C react 2 hours.The reaction solution is put into methanol In (460ml), and leaching gained sediment.The sediment is cleaned with methanol, is dried under reduced pressure and is obtained with 100 DEG C Polyimide powder (26).The acid imide rate of the polyimides is 54%, and number-average molecular weight 17,600, weight average molecular weight are 49,200。

In the NEP (16.7g) mixing E2 (2.23g, 8.92mmol), B1 (1.62g, 5.42mmol), D2 (1.38g, 9.04mmol) with D3 (1.36g, 3.62mmol), after reacting 5 hours with 80 DEG C, E1 (1.75g, 8.92mmol) and NEP are added (8.34g) is reacted 6 hours with 40 DEG C, to obtain the polyamic acid solution that resin solid content concentration is 25 mass %.

After being diluted to 6 mass % to addition NEP in gained polyamic acid solution (30.0g), it is catalyzed as imidizate Agent and add acetic anhydride (3.45g) and pyridine (2.65g), with 60 DEG C react 2 hours.The reaction solution is put into methanol In (460ml), and leaching gained sediment.The sediment is cleaned with methanol, is dried under reduced pressure and is obtained with 100 DEG C Polyimide powder (27).The acid imide rate of the polyimides is 57%, and number-average molecular weight 18,600, weight average molecular weight are 51,500。

Polyimides based polymer of the invention is shown in 2~table of table 4.

[table 2]

* 1: polyamic acid.

[table 3]

* 1: polyamic acid.

[table 4]

* 1: polyamic acid.

" manufacture of aligning agent for liquid crystal of the invention "

In following 1~embodiments of embodiment 19 and 1~comparative example of comparative example 8, the manufacture of aligning agent for liquid crystal is recorded Example.In addition, the aligning agent for liquid crystal is also used to be evaluated.

Aligning agent for liquid crystal of the invention is shown in 5~table of table 7.

Using aligning agent for liquid crystal obtained in examples and comparative examples of the present invention, " aligning agent for liquid crystal is carried out Ink-jet application evaluation ", " production of liquid crystal cells and the evaluation (normal cells) of pre-tilt angle ", " voltage retention is commented Valence (normal cells) ", " evaluation (normal cells) of the mitigation of residual charge " and " production of liquid crystal cells and liquid crystal aligning It evaluates (PSA unit) ".

" evaluation of the ink-jet application of aligning agent for liquid crystal "

At liquid crystal aligning obtained in aligning agent for liquid crystal obtained in the embodiment of the present invention 4 (4), embodiment 9 Aligning agent for liquid crystal (15) obtained in reason agent (9) and embodiment 15 carries out pressure filtration with the molecular filter that aperture is 1 μm, into The evaluation of row ink-jet application.Ink-jet application machine uses HIS-200 (Hitachi Plant Technologies, Ltd. system). About coating, on ITO (tin indium oxide) the vapor deposition substrate through being cleaned with pure water and IPA, using be divided between nozzle 0.423mm, Sweep spacing is 0.5mm, coating speed is 40mm/ seconds, the time from coating until predrying is 60 seconds, predrying is in heat It is carried out on plate with 70 DEG C for 5 minutes conditions.

The painting film property of substrate of the confirmation gained with liquid crystal orientation film.Specifically, by visually observing film under sodium vapor lamp It carries out, the presence or absence of confirmation pin hole.As a result, liquid crystal orientation film obtained in any embodiment does not observe needle on film Hole can obtain the excellent liquid crystal orientation film of film.

" production of liquid crystal cells and the evaluation (normal cells) of pre-tilt angle "

Aligning agent for liquid crystal obtained in examples and comparative examples of the present invention is carried out with the molecular filter that aperture is 1 μm Pressure filtration carries out the production (normal cells) of liquid crystal cells.By the solution be spun on through being cleaned with pure water and IPA 40 × On the ito surface of the substrate (vertical 40mm × horizontal 30mm, thickness 0.7mm) with ITO electrode of 30mm, heated on hot plate with 100 DEG C Processing 5 minutes is cleaned baking oven using thermal cycle type and is heated 30 minutes with 230 DEG C, so that obtaining is the poly- of 100nm with film thickness The ito substrate of acid imide liquid crystal orientation film.It should be noted that at using liquid crystal aligning obtained in the embodiment of the present invention 4 Aligning agent for liquid crystal (15) obtained in aligning agent for liquid crystal (9) obtained in agent (4), embodiment 9 and embodiment 15 is managed, Under the same conditions, the base with liquid crystal orientation film is being made with above-mentioned " evaluation of the ink-jet application of aligning agent for liquid crystal " Plate is cleaned baking oven with thermal cycle type and is heated 30 minutes with 230 DEG C thereafter, to obtain sub- with the polyamides that film thickness is 100nm The ito substrate of amine liquid crystal orientation film.

The brushing device for being 120mm using roller diameter is 1000rpm, roller forward speed in roller revolving speed using rayon cloth Under conditions of being 0.1mm for 50mm/ seconds, intrusion, brushing processing is carried out to the coated surface of the ito substrate.

Prepare 2 ito substrates of the gained with liquid crystal orientation film, clamps 6 μm towards inside with the surface of liquid crystal orientation film Spacer is combined, and is bonded surrounding with sealant to make dummy cell.By decompression injection the normal direction dummy cell in inject to Inlet sealing is obtained liquid crystal cells (normal cells) by column liquid crystal.

It is obtained in aligning agent for liquid crystal obtained in embodiment 1 (1) and comparative example (1) it should be noted that having used Aligning agent for liquid crystal (21) liquid crystal cells in, liquid crystal has used MLC-2003 (MERCK CORPORATION system).Separately Outside, in the unit for having used aligning agent for liquid crystal obtained in embodiment and comparative example in addition to this, liquid crystal is used MLC-6608 (MERCK CORPORATION system).

Then, the pre-tilt angle measurement of the liquid crystal cells (normal cells) is carried out.Pre-tilt angle so measures: carrying out each of liquid crystal To after same sex processing (being heated 5 minutes with 95 DEG C), it is heated and (is heated 5 hours with 120 DEG C), then Liquid crystal cells are measured.

In turn, after carrying out isotropism processing for the liquid crystal cells that make under conditions of same as described above, irradiation with 365nm is scaled 10J/cm²Ultraviolet light after, also liquid crystal cells are measured.It should be noted that pre-tilt angle uses PAS- 301 (ELSICON corporations) are measured at room temperature.In turn, ultraviolet irradiation uses desktop UV solidification equipment (HCT3B28HEX-1) (セ Application ライト corporation) Lai Jinhang.

It is carried out about evaluation relative to the pre-tilt angle after isotropism is handled (after also referred to as Iso processing) of liquid crystal The variation of pre-tilt angle after heat treatment (also referred to as after high-temperature process) and after irradiation ultraviolet light (also referred to as after ultraviolet light irradiation) It is small, then it is regarded as good (8~table of table 10 Iso processing is shown after, the value of pre-tilt angle after high-temperature process and after ultraviolet light irradiation).

8~table of table 10 shows result obtained in embodiment and comparative example.

" evaluation (normal cells) of voltage retention "

It is made under the same conditions using with above-mentioned " production of liquid crystal cells and the evaluation (normal cells) of pre-tilt angle " Liquid crystal cells (normal cells), carry out the evaluation of voltage retention.Specifically, 80 DEG C at a temperature of to utilize above-mentioned side Liquid crystal cells (normal cells) that method obtains apply the 1V voltage of 60 μ s, the voltage after measuring 50ms, by voltage be able to maintain to Which kind of degree is calculated as voltage retention (also referred to as VHR).It should be noted that measurement is surveyed using voltage retention Determine device (VHR-1) (TOYO Corporation system), at voltage (Voltage): ± 1V, pulse width (Pulse Width): 60 μ s, frame period (Flame Period): it is carried out under the setting of 50ms.

In turn, it for the liquid crystal cells after the measurement of the voltage retention after above-mentioned rigid production liquid crystal cells, uses Desktop UV solidification equipment (HCT3B28HEX-1) (セ Application ライト corporation), irradiation are scaled 50J/cm with 365nm²Purple Outside line carries out the measurement of voltage retention under conditions of same as described above.

About evaluation, the voltage retention value after just having made liquid crystal cells is high, and the voltage retention after ultraviolet light irradiation It is worth small relative to the reduction degree of the voltage retention value after rigid production liquid crystal cells, then is regarded as that good (11~table of table 13 is shown The just VHR value after production liquid crystal cells and after ultraviolet light irradiation).

11~table of table 13 shows result obtained in embodiment and comparative example.

" evaluation (normal cells) of the mitigation of residual charge "

It is made under the same conditions using with above-mentioned " production of liquid crystal cells and the evaluation (normal cells) of pre-tilt angle " Liquid crystal cells (normal cells), carry out the evaluation of the mitigation of residual charge.Specifically, applying 30 minutes to liquid crystal cells DC voltage 10V, after making its short circuit 1 second, for the potential measurement generated in liquid crystal cells 1800 seconds.Wherein, using 50 Residual charge value after second, is denoted as the evaluation of the mitigation of residual charge.It should be noted that measurement has used 6254 type liquid crystal objects Property evaluating apparatus (TOYO Corporation system).

In turn, for the liquid crystal cells after the measurement of the residual charge after above-mentioned rigid production liquid crystal cells, table is used Mo(u)ld top half UV solidification equipment (HCT3B28HEX-1) (セ Application ライト corporation), irradiation are scaled 30J/cm with 365nm²It is ultraviolet Line carries out the measurement of residual charge under conditions of same as described above.

About evaluation, just the residual charge value after production liquid crystal cells and after ultraviolet light irradiation is small, then is regarded as good (table 11 ~table 13 show just production liquid crystal cells after and ultraviolet light irradiation after residual charge value).

" production of liquid crystal cells and the evaluation (PSA unit) of liquid crystal aligning "

By aligning agent for liquid crystal (5) obtained in aligning agent for liquid crystal obtained in embodiment 3 (3), embodiment 5, In aligning agent for liquid crystal (8) and embodiment 16 obtained in aligning agent for liquid crystal obtained in embodiment 6 (6), embodiment 8 Obtained aligning agent for liquid crystal (16) is that 1 μm of molecular filter carries out pressure filtration with aperture, carry out the production of liquid crystal cells with The evaluation (PSA unit) of liquid crystal aligning.The solution is spun on through between the 10 × 10mm of center band and pattern with pure water and IPA Every the base of the ITO electrode of the substrate (vertical 40mm × horizontal 30mm, thickness 0.7mm) and 10 × 40mm of center band of 20 μm of ITO electrode The ito surface of plate (vertical 40mm × horizontal 30mm, thickness 0.7mm), is heated 5 minutes on hot plate with 100 DEG C, clear with thermal cycle type Clean baking oven is heated 30 minutes with 230 DEG C, so that film thickness is the polyimide coating film of 100nm.

Substrate with the liquid crystal orientation film is combined with liquid crystal orientation film facing towards the spacer that inside clamps 6 μm, Surrounding is bonded with sealant to make dummy cell.By injecting liquid crystal in decompression injection normal direction dummy cell, the liquid crystal be In nematic liquid crystal (MLC-6608) (MERCK CORPORATION system) with polymerizable compound shown in following formula (1) relative to 100 mass % of nematic liquid crystal (MLC-6608) is sealing obtained from the mode mixed polymerization compound (1) of 0.3 mass % Inlet and obtain liquid crystal cells.

While gained liquid crystal cells are applied with the voltage of exchange 5V, the metal halide lamp that side is 60mW using illumination is clipped 350nm wavelength below, irradiation are scaled 20J/cm with 365nm²Ultraviolet light, obtain the liquid that liquid crystal aligning direction is controlled Brilliant unit (PSA unit).The temperature in irradiation unit when liquid crystal cells are irradiated with ultraviolet light is 50 DEG C.

The response speed of liquid crystal after measuring the preceding irradiation with ultraviolet light of ultraviolet light irradiation of the liquid crystal cells.Response speed is surveyed Determine T90 → T10 of 90%~transmissivity of transmissivity 10%.

Compared with the liquid crystal cells before ultraviolet light irradiation, PSA unit obtained in any embodiment is after uv irradiation The response speeds of liquid crystal cells become faster, therefore confirmed that the differently- oriented directivity of liquid crystal is controlled.In addition, by utilizing polarization Light microscope (ECLIPSE E600WPOL) (Nikon Corporation system) is observed and confirmed: the liquid crystal of any liquid crystal cells is all uniform Ground orientation.

The resin solid content concentration obtained to the synthetic method using synthesis example 1 is the polyamic acid solution of 25 mass % (1) (5.00g) and molten for the polyamic acid of 25 mass % using the resin solid content concentration that the synthetic method of synthesis example 2 obtains Addition NMP (18.2g) and BCS (8.16g) in liquid (2) (3.33g), are stirred 6 hours with 25 DEG C, to obtain liquid crystal aligning processing Agent (1).It does not observe that muddy, precipitation etc. is abnormal in the aligning agent for liquid crystal, is confirmed as uniform solution.

Aligning agent for liquid crystal (1) obtained by use carries out " production of liquid crystal cells and evaluation (the common list of pre-tilt angle Member) ", " evaluation (normal cells) of voltage retention " and " evaluation (normal cells) of the mitigation of residual charge ".

The resin solid content concentration obtained to the synthetic method using synthesis example 3 is the polyamic acid solution of 25 mass % (3) (4.50g) and molten for the polyamic acid of 25 mass % using the resin solid content concentration that the synthetic method of synthesis example 5 obtains Addition NEP (14.4g) and PB (14.1g) in liquid (5) (4.50g), are stirred 6 hours with 25 DEG C, to obtain liquid crystal aligning processing Agent (2).It does not observe that muddy, precipitation etc. is abnormal in the aligning agent for liquid crystal, is confirmed as uniform solution.

Aligning agent for liquid crystal (2) obtained by use carries out " production of liquid crystal cells and evaluation (the common list of pre-tilt angle Member) ", " evaluation (normal cells) of voltage retention " and " evaluation (normal cells) of the mitigation of residual charge ".

The polyimide powder (4) (1.15g) obtained to the synthetic method using synthesis example 4 and the conjunction using synthesis example 6 NEP (21.6g) is added in the polyimide powder (6) (1.15g) obtained at method, with 70 DEG C are stirred 24 hours and keep its molten Solution.PB (14.4g) is added into the solution, is stirred 4 hours with 40 DEG C, to obtain aligning agent for liquid crystal (3).The liquid crystal takes It does not observe that muddy, precipitation etc. is abnormal into inorganic agent, is confirmed as uniform solution.

Aligning agent for liquid crystal (3) obtained by use carries out " production of liquid crystal cells and evaluation (the common list of pre-tilt angle Member) ", " evaluation (normal cells) of voltage retention ", " evaluation (normal cells) of the mitigation of residual charge " and " liquid crystal cells Production and liquid crystal aligning evaluation (PSA unit) ".

The polyimide powder (4) (0.65g) obtained to the synthetic method using synthesis example 4 and the conjunction using synthesis example 6 NEP (14.9g) is added in the polyimide powder (6) (0.43g) obtained at method, with 70 DEG C are stirred 24 hours and keep its molten Solution.BCS (5.97g), PB (8.96g) and K1 (0.032g) are added into the solution, are stirred 6 hours with 40 DEG C, to obtain liquid Brilliant aligning agent (4).It does not observe that muddy, precipitation etc. is abnormal in the aligning agent for liquid crystal, is confirmed as uniform solution.

Aligning agent for liquid crystal (4) obtained by use, carries out " evaluation of the ink-jet application of aligning agent for liquid crystal ", " liquid The production of brilliant unit and the evaluation (normal cells) of pre-tilt angle ", " evaluation (normal cells) of voltage retention " and " residual charge Mitigation evaluation (normal cells) ".

The polyimide powder (7) (1.65g) obtained to the synthetic method using synthesis example 7 and the conjunction using synthesis example 8 NMP (20.3g) is added in the polyimide powder (8) (0.71g) obtained at method, with 70 DEG C are stirred 24 hours and keep its molten Solution.BCS (12.9g) and DME (3.69g) are added into the solution, is stirred 4 hours with 40 DEG C, to obtain liquid crystal aligning processing Agent (5).It does not observe that muddy, precipitation etc. is abnormal in the aligning agent for liquid crystal, is confirmed as uniform solution.

Aligning agent for liquid crystal (5) obtained by use carries out " production of liquid crystal cells and evaluation (the common list of pre-tilt angle Member) ", " evaluation (normal cells) of voltage retention ", " evaluation (normal cells) of the mitigation of residual charge " and " liquid crystal cells Production and liquid crystal aligning evaluation (PSA unit) ".

The resin solid content concentration obtained to the synthetic method using synthesis example 9 is the polyamic acid solution of 25 mass % (9) (3.50g) and molten for the polyamic acid of 25 mass % using the resin solid content concentration that the synthetic method of synthesis example 5 obtains Addition NEP (14.0g), PB (10.3g) and EC (3.43g) in liquid (5) (5.25g), are stirred 6 hours with 25 DEG C, to obtain liquid Brilliant aligning agent (6).It does not observe that muddy, precipitation etc. is abnormal in the aligning agent for liquid crystal, is confirmed as uniform solution.

Aligning agent for liquid crystal (6) obtained by use carries out " production of liquid crystal cells and evaluation (the common list of pre-tilt angle Member) ", " evaluation (normal cells) of voltage retention ", " evaluation (normal cells) of the mitigation of residual charge " and " liquid crystal cells Production and liquid crystal aligning evaluation (PSA unit) ".

To addition NEP in the polyimide powder (10) (1.75g) that the synthetic method using synthesis example 10 obtains (15.0g), with 70 DEG C are stirred 24 hours and are made it dissolve.PB (11.0g) and DME (1.37g) are added, into the solution with 40 DEG C Stirring 4 hours, to obtain solution.

On the other hand, NEP is added in the polyimide powder (6) (0.44g) that the synthetic method of Xiang Liyong synthesis example 6 obtains (3.80g), with 70 DEG C are stirred 24 hours and are made it dissolve.PB (2.70g) and DME (0.34g) are added, into the solution with 40 DEG C Stirring 4 hours, to obtain solution.

2 kinds of solution obtained above is mixed, further adds K1 (0.153g), is stirred 6 hours with 40 DEG C, to obtain Liquid crystal matches aligning agent (7).It does not observe that muddy, precipitation etc. is abnormal in the aligning agent for liquid crystal, is confirmed as uniform molten Liquid.

Aligning agent for liquid crystal (7) obtained by use carries out " production of liquid crystal cells and evaluation (the common list of pre-tilt angle Member) ", " evaluation (normal cells) of voltage retention " and " evaluation (normal cells) of the mitigation of residual charge ".

The polyimide powder (11) (0.75g) that obtains to the synthetic method using synthesis example 11 and utilize synthesis example 8 Addition NMP (6.71g) and NEP (13.4g) in the polyimide powder (8) (1.39g) that synthetic method obtains, with 70 DEG C of stirrings 24 Hour and make it dissolve.PB (13.4g) and K1 (0.107g) are added into the solution, are stirred 6 hours with 40 DEG C, to obtain liquid Brilliant aligning agent (8).It does not observe that muddy, precipitation etc. is abnormal in the aligning agent for liquid crystal, is confirmed as uniform solution.

Aligning agent for liquid crystal (8) obtained by use carries out " production of liquid crystal cells and evaluation (the common list of pre-tilt angle Member) ", " evaluation (normal cells) of voltage retention ", " evaluation (normal cells) of the mitigation of residual charge " and " liquid crystal cells Production and liquid crystal aligning evaluation (PSA unit) ".

The polyimide powder (11) (0.55g) that obtains to the synthetic method using synthesis example 11 and utilize synthesis example 8 Addition NEP (15.2g) and γ-BL (3.79g) in the polyimide powder (8) (0.83g) that synthetic method obtains, are stirred with 70 DEG C 24 hours and make it dissolve.PB (15.2g) and DME (3.79g) are added into the solution, are stirred 4 hours with 40 DEG C, to obtain Aligning agent for liquid crystal (9).It does not observe that muddy, precipitation etc. is abnormal in the aligning agent for liquid crystal, is confirmed as uniform solution.

Aligning agent for liquid crystal (9) obtained by use, carries out " evaluation of the ink-jet application of aligning agent for liquid crystal ", " liquid The production of brilliant unit and the evaluation (normal cells) of pre-tilt angle ", " evaluation (normal cells) of voltage retention " and " residual charge Mitigation evaluation (normal cells) ".

To addition NMP (1.73g) in the polyimide powder (4) (1.10g) that the synthetic method using synthesis example 4 obtains and NEP (6.90g), with 70 DEG C are stirred 24 hours and are made it dissolve.BCS (1.73g) and PB (6.90g) are added into the solution, with 40 DEG C are stirred 4 hours, to obtain solution.

On the other hand, addition in the polyimide powder (12) (1.10g) that the synthetic method of Xiang Liyong synthesis example 12 obtains NMP (1.73g) and NEP (6.90g), with 70 DEG C are stirred 24 hours and are made it dissolve.Into the solution add BCS (1.73g) and PB (6.90g) is stirred 4 hours with 40 DEG C, to obtain solution.

2 kinds of solution obtained above is mixed, is stirred 6 hours with 25 DEG C, to obtain aligning agent for liquid crystal (10).It should It does not observe that muddy, precipitation etc. is abnormal in aligning agent for liquid crystal, is confirmed as uniform solution.

Aligning agent for liquid crystal (10) obtained by use carries out " production of liquid crystal cells and evaluation (the common list of pre-tilt angle Member) ", " evaluation (normal cells) of voltage retention " and " evaluation (normal cells) of the mitigation of residual charge ".

The polyimide powder (13) (1.25g) that obtains to the synthetic method using synthesis example 13 and utilize synthesis example 8 Addition NEP (13.1g) and γ-BL (3.26g) in the polyimide powder (8) (0.83g) that synthetic method obtains, are stirred with 70 DEG C 24 hours and make it dissolve.BCS (13.1g) and EC (3.26g) are added into the solution, are stirred 4 hours with 40 DEG C, to obtain Aligning agent for liquid crystal (11).It does not observe that muddy, precipitation etc. is abnormal in the aligning agent for liquid crystal, is confirmed as uniform molten Liquid.

Aligning agent for liquid crystal (11) obtained by use carries out " production of liquid crystal cells and evaluation (the common list of pre-tilt angle Member) ", " evaluation (normal cells) of voltage retention " and " evaluation (normal cells) of the mitigation of residual charge ".

The polyimide powder (10) (0.65g) that obtains to the synthetic method using synthesis example 10 and utilize synthesis example 8 Addition NMP (17.0g) and γ-BL (1.70g) in the polyimide powder (8) (1.52g) that synthetic method obtains, are stirred with 70 DEG C 24 hours and make it dissolve.BCS (6.79g) and PB (8.49g) are added into the solution, are stirred 4 hours with 40 DEG C, to obtain Aligning agent for liquid crystal (12).It does not observe that muddy, precipitation etc. is abnormal in the aligning agent for liquid crystal, is confirmed as uniform molten Liquid.

Aligning agent for liquid crystal (12) obtained by use carries out " production of liquid crystal cells and evaluation (the common list of pre-tilt angle Member) ", " evaluation (normal cells) of voltage retention " and " evaluation (normal cells) of the mitigation of residual charge ".

The resin solid content concentration obtained to the synthetic method using synthesis example 15 is that the polyamic acid of 25 mass % is molten Liquid (15) (4.50g) and using synthesis example 16 the obtained resin solid content concentration of synthetic method be 25 mass % polyamide Addition NMP (14.4g), BCS (3.53g), PB (10.6g) and K1 (0.225g) in acid solution (16) (4.50g), are stirred with 40 DEG C 6 hours, to obtain aligning agent for liquid crystal (13).Do not observe that muddy, precipitation etc. is abnormal in the aligning agent for liquid crystal, really Think uniform solution.

Aligning agent for liquid crystal (13) obtained by use carries out " production of liquid crystal cells and evaluation (the common list of pre-tilt angle Member) ", " evaluation (normal cells) of voltage retention " and " evaluation (normal cells) of the mitigation of residual charge ".

The polyimide powder (7) (0.90g) obtained to the synthetic method using synthesis example 7 and the conjunction using synthesis example 17 NEP (15.9g) is added in the polyimide powder (17) (1.35g) obtained at method, with 70 DEG C are stirred 24 hours and keep its molten Solution.BCS (5.29g) and PB (14.1g) are added into the solution, are stirred 4 hours with 40 DEG C, to obtain aligning agent for liquid crystal (14).It does not observe that muddy, precipitation etc. is abnormal in the aligning agent for liquid crystal, is confirmed as uniform solution.

Aligning agent for liquid crystal (14) obtained by use carries out " production of liquid crystal cells and evaluation (the common list of pre-tilt angle Member) ", " evaluation (normal cells) of voltage retention " and " evaluation (normal cells) of the mitigation of residual charge ".

The polyimide powder (7) (0.55g) obtained to the synthetic method using synthesis example 7 and the conjunction using synthesis example 17 Addition NMP (3.79g) and NEP (15.2g) in the polyimide powder (17) (0.83g) obtained at method, with 70 DEG C of stirrings 24 Hour and make it dissolve.PB (19.0g) is added into the solution, is stirred 4 hours with 40 DEG C, to obtain aligning agent for liquid crystal (15).It does not observe that muddy, precipitation etc. is abnormal in the aligning agent for liquid crystal, is confirmed as uniform solution.

Aligning agent for liquid crystal (15) obtained by use, carries out " evaluation of the ink-jet application of aligning agent for liquid crystal ", " liquid The production of brilliant unit and the evaluation (normal cells) of pre-tilt angle ", " evaluation (normal cells) of voltage retention " and " residual charge Mitigation evaluation (normal cells) ".

To addition NMP in the polyimide powder (18) (1.25g) that the synthetic method using synthesis example 18 obtains (8.82g), with 70 DEG C are stirred 24 hours and are made it dissolve.BCS (2.94g) and PB (7.86g) are added, into the solution with 40 DEG C Stirring 4 hours, to obtain solution.

On the other hand, addition in the polyimide powder (17) (0.83g) that the synthetic method of Xiang Liyong synthesis example 17 obtains NMP (5.88g), with 70 DEG C are stirred 24 hours and are made it dissolve.BCS (1.96g) and PB (5.24g) are added into the solution, with 40 DEG C are stirred 4 hours, to obtain solution.

2 kinds of solution obtained above is mixed, is stirred 4 hours with 25 DEG C, to obtain aligning agent for liquid crystal (16).It should It does not observe that muddy, precipitation etc. is abnormal in aligning agent for liquid crystal, is confirmed as uniform solution.

Aligning agent for liquid crystal (16) obtained by use carries out " production of liquid crystal cells and evaluation (the common list of pre-tilt angle Member) ", " evaluation (normal cells) of voltage retention ", " evaluation (normal cells) of the mitigation of residual charge " and " liquid crystal cells Production and liquid crystal aligning evaluation (PSA unit) ".

To addition K1 in the aligning agent for liquid crystal (16) (20.0g) that the preparation method using embodiment 16 obtains (0.06g) is stirred 6 hours with 40 DEG C, to obtain aligning agent for liquid crystal (17).It is not observed in the aligning agent for liquid crystal Muddy, precipitation etc. is abnormal, is confirmed as uniform solution.

Aligning agent for liquid crystal (17) obtained by use carries out " production of liquid crystal cells and evaluation (the common list of pre-tilt angle Member) ", " evaluation (normal cells) of voltage retention " and " evaluation (normal cells) of the mitigation of residual charge ".

The polyimide powder (19) (0.45g) that obtains to the synthetic method using synthesis example 19 and utilize synthesis example 6 NEP (21.2g) is added in the polyimide powder (6) (1.80g) that synthetic method obtains, with 70 DEG C are stirred 24 hours and keep its molten Solution.BCS (3.53g) and PB (10.6g) are added into the solution, are stirred 4 hours with 40 DEG C, to obtain aligning agent for liquid crystal (18).It does not observe that muddy, precipitation etc. is abnormal in the aligning agent for liquid crystal, is confirmed as uniform solution.

Aligning agent for liquid crystal (18) obtained by use carries out " production of liquid crystal cells and evaluation (the common list of pre-tilt angle Member) ", " evaluation (normal cells) of voltage retention " and " evaluation (normal cells) of the mitigation of residual charge ".

The polyimide powder (19) (1.63g) that obtains to the synthetic method using synthesis example 19 and utilize synthesis example 5 The resin solid content concentration that synthetic method obtains is that NEP is added in the polyamic acid solution (5) (6.50g) of 25 mass % (19.4g), with 70 DEG C are stirred 24 hours and are made it dissolve.BCS (6.47g) and PB (6.47g) are added, into the solution with 40 DEG C Stirring 4 hours, to obtain aligning agent for liquid crystal (19).Do not observe that muddy, precipitation etc. is different in the aligning agent for liquid crystal Often, it is confirmed as uniform solution.

Aligning agent for liquid crystal (19) obtained by use carries out " production of liquid crystal cells and evaluation (the common list of pre-tilt angle Member) ", " evaluation (normal cells) of voltage retention " and " evaluation (normal cells) of the mitigation of residual charge ".

The resin solid content concentration obtained to the synthetic method using synthesis example 20 is that the polyamic acid of 25 mass % is molten Liquid (20) (4.95g) and using synthesis example 21 the obtained resin solid content concentration of synthetic method be 25 mass % polyamide Addition NMP (18.0g) and BCS (8.08g) in acid solution (21) (3.30g), are stirred 6 hours with 25 DEG C, are taken to obtain liquid crystal To inorganic agent (20).It does not observe that muddy, precipitation etc. is abnormal in the aligning agent for liquid crystal, is confirmed as uniform solution.

Aligning agent for liquid crystal (20) obtained by use carries out " production of liquid crystal cells and evaluation (the common list of pre-tilt angle Member) ", " evaluation (normal cells) of voltage retention " and " evaluation (normal cells) of the mitigation of residual charge ".

The resin solid content concentration obtained to the synthetic method using synthesis example 3 is the polyamic acid solution of 25 mass % (3) (4.50g) and the polyamic acid for being 25 mass % using the resin solid content concentration that the synthetic method of synthesis example 24 obtains Addition NEP (14.4g) and PB (14.1g) in solution (24) (4.50g), are stirred 6 hours with 25 DEG C, to obtain at liquid crystal aligning It manages agent (21).It does not observe that muddy, precipitation etc. is abnormal in the aligning agent for liquid crystal, is confirmed as uniform solution.

Aligning agent for liquid crystal (21) obtained by use carries out " production of liquid crystal cells and evaluation (the common list of pre-tilt angle Member) ", " evaluation (normal cells) of voltage retention " and " evaluation (normal cells) of the mitigation of residual charge ".

The resin solid content concentration obtained to the synthetic method using synthesis example 22 is that the polyamic acid of 25 mass % is molten Liquid (22) (4.50g) and using synthesis example 5 the obtained resin solid content concentration of synthetic method be 25 mass % polyamide Addition NEP (14.4g) and PB (14.1g) in acid solution (5) (4.50g), are stirred 6 hours with 25 DEG C, to obtain liquid crystal aligning Inorganic agent (22).It does not observe that muddy, precipitation etc. is abnormal in the aligning agent for liquid crystal, is confirmed as uniform solution.

Aligning agent for liquid crystal (22) obtained by use carries out " production of liquid crystal cells and evaluation (the common list of pre-tilt angle Member) ", " evaluation (normal cells) of voltage retention " and " evaluation (normal cells) of the mitigation of residual charge ".

The resin solid content concentration obtained to the synthetic method using synthesis example 22 is that the polyamic acid of 25 mass % is molten Liquid (22) (4.50g) and using synthesis example 24 the obtained resin solid content concentration of synthetic method be 25 mass % polyamide Addition NEP (14.4g) and PB (14.1g) in acid solution (24) (4.50g), are stirred 6 hours with 25 DEG C, to obtain liquid crystal aligning Inorganic agent (23).It does not observe that muddy, precipitation etc. is abnormal in the aligning agent for liquid crystal, is confirmed as uniform solution.

Aligning agent for liquid crystal (23) obtained by use carries out " production of liquid crystal cells and evaluation (the common list of pre-tilt angle Member) ", " evaluation (normal cells) of voltage retention " and " evaluation (normal cells) of the mitigation of residual charge ".

The polyimide powder (4) (1.10g) obtained to the synthetic method using synthesis example 4 and the conjunction using synthesis example 25 NEP (20.7g) is added in the polyimide powder (25) (1.10g) obtained at method, with 70 DEG C are stirred 24 hours and keep its molten Solution.PB (13.8g) is added into the solution, is stirred 4 hours with 40 DEG C, to obtain aligning agent for liquid crystal (24).The liquid crystal It does not observe that muddy, precipitation etc. is abnormal in aligning agent, is confirmed as uniform solution.

Aligning agent for liquid crystal (24) obtained by use carries out " production of liquid crystal cells and evaluation (the common list of pre-tilt angle Member) ", " evaluation (normal cells) of voltage retention " and " evaluation (normal cells) of the mitigation of residual charge ".

The polyimide powder (23) (1.10g) that obtains to the synthetic method using synthesis example 23 and utilize synthesis example 6 NEP (20.7g) is added in the polyimide powder (6) (1.10g) that synthetic method obtains, with 70 DEG C are stirred 24 hours and keep its molten Solution.PB (13.8g) is added into the solution, is stirred 4 hours with 40 DEG C, to obtain aligning agent for liquid crystal (25).The liquid crystal It does not observe that muddy, precipitation etc. is abnormal in aligning agent, is confirmed as uniform solution.

Aligning agent for liquid crystal (25) obtained by use carries out " production of liquid crystal cells and evaluation (the common list of pre-tilt angle Member) ", " evaluation (normal cells) of voltage retention " and " evaluation (normal cells) of the mitigation of residual charge ".

The polyimide powder (23) (1.10g) that obtains to the synthetic method using synthesis example 23 and utilize synthesis example 25 NEP (20.7g) is added in the polyimide powder (25) (1.10g) that synthetic method obtains, with 70 DEG C are stirred 24 hours and make it Dissolution.PB (13.8g) is added into the solution, is stirred 4 hours with 40 DEG C, to obtain aligning agent for liquid crystal (26).The liquid It does not observe that muddy, precipitation etc. is abnormal in brilliant aligning agent, is confirmed as uniform solution.

Aligning agent for liquid crystal (26) obtained by use carries out " production of liquid crystal cells and evaluation (the common list of pre-tilt angle Member) ", " evaluation (normal cells) of voltage retention " and " evaluation (normal cells) of the mitigation of residual charge ".

The polyimide powder (26) (1.10g) that obtains to the synthetic method using synthesis example 26 and utilize synthesis example 27 NEP (20.7g) is added in the polyimide powder (27) (1.10g) that synthetic method obtains, with 70 DEG C are stirred 24 hours and make it Dissolution.PB (13.8g) is added into the solution, is stirred 4 hours with 40 DEG C, to obtain aligning agent for liquid crystal (27).The liquid It does not observe that muddy, precipitation etc. is abnormal in brilliant aligning agent, is confirmed as uniform solution.

Aligning agent for liquid crystal (27) obtained by use carries out " production of liquid crystal cells and evaluation (the common list of pre-tilt angle Member) ", " evaluation (normal cells) of voltage retention " and " evaluation (normal cells) of the mitigation of residual charge ".

[table 5]

* 1: indicating the import volume (mass parts) of particular polymers (A) relative to whole 100 mass parts of polymer.

* 2: indicating the import volume (mass parts) of particular polymers (B) relative to whole 100 mass parts of polymer.

* 3: indicating other polymer phases for the import volume (mass parts) of whole 100 mass parts of polymer.

* 4: indicating import volume (mass parts) of the cross-linked compound relative to whole 100 mass parts of polymer.

* 5: indicating import volume (mass parts) of each solvent relative to whole 100 mass parts of solvent.

* 6: indicating whole polymer ratio shared in aligning agent for liquid crystal.

[table 6]

* 5: indicating the import volume (mass parts) of each 100 mass parts of solvent whole solvent.

[table 7]

[table 8]

[table 9]

[table 10]

[table 11]

[table 12]

[table 13]

From the above results: compared with the aligning agent for liquid crystal of comparative example, the liquid crystal aligning of the embodiment of the present invention In inorganic agent, even if carrying out high-temperature process and ultraviolet light irradiation to liquid crystal cells, stable pre-tilt angle is also shown.And then it presents such as Lower result: even if carrying out ultraviolet light irradiation, the reduction of voltage retention, and the residual accumulated by DC voltage can also be inhibited Charge quickly mitigates.That is, aligning agent for liquid crystal of the invention will form after long-time is exposed to high temperature and light irradiation The liquid crystal orientation film of pre-tilt angle can be shown to stablize, also, will form and can press down long-time is exposed to after light irradiation The liquid crystal orientation film that voltage retention reduction processed and the residual charge accumulated by DC voltage quickly mitigate.

Specifically, having used the aligning agent for liquid crystal of particular polymers of the invention (A) and particular polymers (B) The comparison of embodiment and the embodiment for the aligning agent for liquid crystal that one of them is used only, i.e., embodiment 2 and comparative example 2 or compared with The comparison of the comparison of example 3 and embodiment 3 and comparative example 5 or comparative example 6.These only used the comparison of particular polymers (A) Example or the comparative example that only used particular polymers (B) irradiate compared with corresponding embodiment especially relative to ultraviolet light Voltage retention is greatly reduced, and furthermore the value of residual charge also becomes larger.

In addition, having used the implementation of the aligning agent for liquid crystal of particular polymers of the invention (A) and particular polymers (B) Example with used polymer without the structure of the invention with tertiary N atom and the polymer without specific structure (2) The comparison of the comparative example of aligning agent for liquid crystal, i.e. embodiment 1 and comparative example 1, the comparison of embodiment 2 and comparative example 4, Yi Jishi Apply the comparison of example 3 Yu comparative example 7.These comparative examples are compared with corresponding embodiment, especially relative to the electricity of ultraviolet light irradiation Pressure conservation rate is greatly reduced, and furthermore the value of residual charge also becomes larger.

Also, the implementation of the aligning agent for liquid crystal of particular polymers of the invention (A) and particular polymers (B) is used The comparison of example and the comparative example for the aligning agent for liquid crystal for having used the polymer with previous type side-chain structure, i.e. embodiment 3 With the comparison of comparative example 8.Pre-tilt angle of the comparative example compared with corresponding embodiment, after carrying out high-temperature process and ultraviolet light irradiation Amplitude of variation it is larger, and relative to ultraviolet light irradiation voltage retention be greatly reduced, furthermore the value of residual charge also becomes larger. Wherein, the reduction of especially voltage retention is obvious.

Industrial availability

Aligning agent for liquid crystal of the invention is capable of providing can express long-time is exposed to after high temperature and light irradiation The liquid crystal orientation film of stable pre-tilt angle out.Further, it is possible to which providing can inhibit voltage to protect long-time is exposed to after light irradiation The liquid crystal orientation film that holdup reduction and the residual charge accumulated by DC voltage quickly mitigate.And, it is possible to provide have above-mentioned The aligning agent for liquid crystal that the liquid crystal of liquid crystal orientation film indicates element, is capable of providing above-mentioned liquid crystal orientation film.

Thus, there is the liquid crystal of the liquid crystal orientation film obtained by aligning agent for liquid crystal of the invention to indicate the reliable of element Property is excellent, can be suitably employed in the LCD TV etc. of big picture and high-resolution, for TN element, STN element, TFT liquid crystal cell, Especially the liquid crystal of vertical orientating type indicates that element is useful.

In turn, the liquid crystal orientation film obtained by aligning agent for liquid crystal of the invention is for needing to indicate member in production liquid crystal The liquid crystal that ultraviolet light is irradiated when part indicates that element is also useful.That is, indicating that element is also useful for following liquid crystal: having Element is indicated with liquid crystal layer between a pair of of substrate of standby electrode and via the liquid crystal of following process manufacture, in aforementioned a pair of of substrate Between configure liquid-crystal composition, the liquid-crystal composition includes gathering of polymerize by least one of active energy beam and heat Conjunction property compound polymerize aforementioned polymeric compound while to voltage is applied between former electrodes；And having electrode Element is indicated with liquid crystal layer between a pair of of substrate and via the liquid crystal of following process manufacture, is configured between aforementioned a pair of of substrate Liquid crystal orientation film, the liquid crystal orientation film include the polymerism base polymerizeing by least one of active energy beam and heat Group makes aforementioned polymeric radical polymerisation while to voltage is applied between former electrodes.

Claims

1. a kind of aligning agent for liquid crystal contains following (A) ingredients and (B) ingredient:

(A) ingredient: the polymer containing at least any one in polyimide precursor and polyimides, the polyimides Precursor and polyimides have the structure with nitrogen-atoms,

(B) ingredient: the polymer containing at least any one in polyimide precursor and polyimides, the polyimides Precursor and polyimides have structure shown in following formula [2],

Wherein, at least either in the polymer of (A) ingredient and (B) ingredient contains structure shown in following formula [3],

In formula [2], Y¹And Y⁷Singly-bound is each independently represented, alkylidene ,-O- ,-N (R selected from carbon number 1~10¹)-、-CON (R²)-、-N(R³)CO-、-CH₂At least one kind of organic group in O- ,-COO- and-OCO-, wherein R¹Indicate hydrogen atom or carbon number 1~3 alkylidene, R²Indicate the alkylidene of hydrogen atom or carbon number 1~3, R³Indicate the alkylidene of hydrogen atom or carbon number 1~3；Y² And Y⁶Each independently represent the alkylidene of carbon number 1~10；Y³And Y⁵Each independently represent the Asia of hydrogen atom or carbon number 1~10 Alkyl；Y⁴Indicate oxygen atom or sulphur atom,

In formula [3], B¹Indicate singly-bound ,-(CH₂)_a-、-O-、-CH₂O- ,-COO- or-OCO-, wherein the integer that a is 1~15；B² Indicate singly-bound or-(CH₂)_b, wherein the integer that b is 1~15；B³Indicate singly-bound ,-(CH₂)_c-、-O-、-CH₂O- ,-COO- or- OCO-, wherein the integer that c is 1~15；B⁴It indicates the divalent cyclic group in phenyl ring, cyclohexane ring or heterocycle or has The divalent organic group of the carbon number 17~51 of steroid skeleton, any hydrogen atom on the cyclic group is optionally by carbon number 1~3 Alkyl, the alkoxy of carbon number 1~3, carbon number 1~3 replace containing fluoroalkyl, the fluoroalkoxy of carbon number 1~3 or fluorine atom； B⁵Indicate the divalent cyclic group in phenyl ring, cyclohexane ring or heterocycle, any hydrogen atom optionally quilt on these cyclic groups The alkyl of carbon number 1~3, the alkoxy of carbon number 1~3, carbon number 1~3 it is former containing fluoroalkyl, the fluoroalkoxy of carbon number 1~3 or fluorine Son replaces；N indicates 0~4 integer；B⁶Indicate the alkyl of carbon number 1~18, carbon number 1~18 containing fluoroalkyl, carbon number 1~18 The fluoroalkoxy of alkoxy or carbon number 1~18.

2. aligning agent for liquid crystal according to claim 1, wherein the structure with nitrogen-atoms in (A) ingredient is At least one kind of structure in structure shown in following formula [1a]~formula [1c],

In formula [1a], X¹Indicate phenyl ring or nitrogenous heteroaromatic, X²Indicate hydrogen atom or by the aliphatic group of carbon number 1~12 Substituted disubstituted amido；In formula [1b], X³And X⁷It each independently represents with 6~15 carbon atoms and there is 1~2 benzene The aromatic group of ring, X⁴And X⁶Each independently represent the alkylidene of hydrogen atom or carbon number 1~5, X⁵Indicate the Asia of carbon number 2~5 Alkyl or xenyl, m indicate 0 or 1 integer；In formula [1c], X⁸And X¹⁰Each independently represent selected from following formula [1c-a] and At least one kind of structure in structure shown in formula [1c-b], X⁹Indicate the alkylidene or phenyl ring of carbon number 1~5,

3. according to claim 1 or aligning agent for liquid crystal as claimed in claim 2, wherein the polymer of (A) ingredient is Diamine compound shown in following formula [1-1] is used for polymer obtained from a part of raw material,

In formula [1-1], X^AIndicate the organic group at least one kind of structure for having in structure shown in above-mentioned formula [1a]~formula [1c] Group, A¹And A²Each independently represent the alkylidene of hydrogen atom or carbon number 1~5.

4. aligning agent for liquid crystal according to claim 3, be by the diamine compound following formula [1a-1]~ Diamine compound shown in formula [1c-1] is used for polymer obtained from a part of raw material,

In formula [1a-1], X¹Indicate phenyl ring or nitrogenous heteroaromatic, X²Indicate hydrogen atom or by the fatty group of carbon number 1~12 The disubstituted amido that group replaces；In formula [1b-1], X³And X⁷It each independently represents with 6~15 carbon atoms and has 1~2 The aromatic group of a phenyl ring, X⁴And X⁶Each independently represent the alkylidene of hydrogen atom or carbon number 1~5, X⁵Indicate carbon number 2~5 Alkylidene or xenyl, m indicate 0 or 1 integer；In formula [1c-1], X⁸And X¹⁰It each independently represents selected from above-mentioned formula At least one kind of structure in structure shown in [1c-a] and formula [1c-b], X⁹Indicate the alkylidene or phenyl ring of carbon number 1~5；Formula [1a-1] In~formula [1c-1], A¹~A⁶Each independently represent the alkylidene of hydrogen atom or carbon number 1~5.

5. aligning agent for liquid crystal according to claim 4, wherein the diamine compound is selected from following formula [1-1a] At least one kind of diamine compound in diamine compound shown in~formula [1-4a],

In formula [1-3a], R¹Indicate the alkylidene of hydrogen atom or carbon number 1~5；In formula [1-4a], n indicates 1~10 integer；Formula In [1-1a]~formula [1-4a], A¹~A⁸Each independently represent the alkylidene of hydrogen atom or carbon number 1~5.

6. according to claim 1 or aligning agent for liquid crystal as claimed in claim 2, wherein the polymer of (B) ingredient is Diamine compound shown in following formula [2-1] is used for polymer obtained from a part of raw material,

In formula [2-1], Y^AIndicate the organic group with structure shown in previously described formula [2], A¹And A²Each independently represent hydrogen atom Or the alkylidene of carbon number 1~5.

7. it is shown in following formula [2a] that aligning agent for liquid crystal according to claim 6, which is by the diamine compound, Diamine compound for raw material a part obtained from polymer,

In formula [2a], Y¹And Y⁷Singly-bound is each independently represented, alkylidene ,-O- ,-N (R selected from carbon number 1~10¹)-、-CON (R²)-、-N(R³)CO-、-CH₂At least one kind of organic group in O- ,-COO- and-OCO-, wherein R¹Indicate hydrogen atom or carbon number 1~3 alkylidene, R²Indicate the alkylidene of hydrogen atom or carbon number 1~3, R³Indicate the alkylidene of hydrogen atom or carbon number 1~3；Y² And Y⁶Each independently represent the alkylidene of carbon number 1~10；Y³And Y⁵Each independently represent the Asia of hydrogen atom or carbon number 1~10 Alkyl；Y⁴Indicate oxygen atom or sulphur atom；A¹And A²Each independently represent the alkylidene of hydrogen atom or carbon number 1~5.

8. aligning agent for liquid crystal according to claim 7, wherein the diamine compound is selected from following formula [2-1a] At least one kind of diamine compound in diamine compound shown in~formula [2-3a],

In formula [2-1a]~formula [2-3a], A¹~A⁶Each independently represent the alkylidene of hydrogen atom or carbon number 1~5.

9. according to claim 1 or aligning agent for liquid crystal as claimed in claim 2, wherein (A) ingredient and (B) ingredient In at least either polymer by diamine compound shown in following formula [3a] be used for raw material a part,

In formula [3a], B indicates above-mentioned formula [3]；A¹And A²Each independently represent the alkylidene of hydrogen atom or carbon number 1~5；M is indicated 1~4 integer.

10. according to claim 1 or aligning agent for liquid crystal as claimed in claim 2, wherein the polymer of (A) ingredient The polymer of (B) ingredient is selected from using polyimide precursor obtained from tetracarboxylic acid sour component shown in following formula [4] and poly- At least one kind of polymer in acid imide,

In formula [4], Z indicates at least one kind of structure in structure shown in following formula [4a]~formula [4k],

In formula [4a], Z¹~Z⁴Indicate hydrogen atom, methyl, ethyl, propyl, chlorine atom or phenyl ring, it is optionally identical or different each other； In formula [4g], Z⁵And Z⁶Indicate hydrogen atom or methyl, it is optionally identical or different each other.

11. aligning agent for liquid crystal according to claim 10, wherein the tetracarboxylic acid sour component is the Z in the formula [4] For the tetracarboxylic acid sour component of at least one kind of structure in structure shown in the formula [4a] and formula [4e]~formula [4g].

12. aligning agent for liquid crystal according to claim 4, wherein in the polymer of (A) ingredient, the formula Diamine compound shown in [1a-1]~formula [1c-1] is 5 moles of %~95 mole % in 100 moles of % of whole diamine components.

13. aligning agent for liquid crystal according to claim 7, wherein in the polymer of (B) ingredient, the formula Diamine compound shown in [2a] is 5 moles of %~95 mole % in 100 moles of % of whole diamine components.

14. according to claim 1 or aligning agent for liquid crystal as claimed in claim 2, wherein the polymer of (B) ingredient 100 mass parts of polymer relative to (A) ingredient are 0.5 mass parts~950 mass parts.

15. according to claim 1 or aligning agent for liquid crystal as claimed in claim 2, wherein as aligning agent for liquid crystal Solvent contains at least one kind of solvent in n-methyl-2-pyrrolidone, N- ethyl-2-pyrrolidone and gamma-butyrolacton.

16. according to claim 1 or aligning agent for liquid crystal as claimed in claim 2, wherein as aligning agent for liquid crystal Solvent, containing selected from 1- hexanol, cyclohexanol, 1,2- ethylene glycol, 1,2-PD, glycol monobutyl ether, ethylene glycol monobutyl At least one kind of solvent in ether and dipropylene glycol dimethyl ether.

17. according to claim 1 or aligning agent for liquid crystal as claimed in claim 2, wherein include in aligning agent for liquid crystal At least one kind of cross-linked compound in following cross-linked compound: there is epoxy group, isocyanate group, oxetanes The cross-linked compound of base or cyclocarbonate radical；With the group for selecting free hydroxyl, hydroxy alkyl or low-grade alkoxy alkyl composition In at least one kind of substituent group cross-linked compound；And the cross-linked compound with polyunsaturated bond.

18. a kind of liquid crystal orientation film is the aligning agent for liquid crystal as described in any one of 1~claim 17 of claim It obtains.

19. a kind of liquid crystal orientation film is handled using liquid crystal aligning described in any one of 1~claim 17 of claim Agent is as obtained from ink-jet method.

20. a kind of liquid crystal indicates element, with liquid crystal orientation film described in claim 18 or claim 19.

21. according to claim 18 or claim 19 described in liquid crystal orientation film, which is characterized in that it be used to have electricity Element is indicated with liquid crystal layer between a pair of of substrate of pole and via the liquid crystal of following process manufacture: between the pair of substrate Liquid-crystal composition is configured, the liquid-crystal composition includes the polymerism polymerizeing by least one of active energy beam and heat Compound polymerize the polymerizable compound while to voltage is applied between the electrode.

22. a kind of liquid crystal indicates element, which is characterized in that have liquid crystal orientation film described in claim 21.

23. according to claim 18 or claim 19 described in liquid crystal orientation film, which is characterized in that it be used to have electricity Element is indicated with liquid crystal layer between a pair of of substrate of pole and via the liquid crystal of following process manufacture: between the pair of substrate Liquid crystal orientation film is configured, the liquid crystal orientation film includes the polymerism polymerizeing by least one of active energy beam and heat Group polymerize the polymerizable group while to voltage is applied between the electrode.

24. a kind of liquid crystal indicates element, which is characterized in that have liquid crystal orientation film described in claim 23.